Molecules having one hydrophobic group and two identical hydrophilic ionic groups and compositions thereof and methods of preparation thereof

ABSTRACT

A novel class of compounds is described here. The disclosed novel compounds have one hydrophilic group and two identical hydrophilic ionic groups. The two hydrophilic groups of the disclosed compounds contain or end with a cationic or anionic charged group. The disclosed novel compounds herein can be used as surfactants in an article, product, or composition, or for some other purposes. A method to synthesize the disclosed novel compounds is also described.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority and is related to U.S. ProvisionalApplication Ser. No. 62/552,108, filed on Aug. 30, 2017 and entitled“MOLECULES HAVING ONE HYDROPHOBIC AND TWO IDENTICAL HYDROPHILIC GROUPSAND COMPOSITIONS THEREOF AND METHODS OF PREPARATION THEREOF.” The entirecontents of this patent application are hereby expressly incorporatedherein by reference including, without limitation, the specification,claims, and abstract, as well as any figures, tables, or drawingsthereof.

FIELD OF THE INVENTION

The present disclosure relates generally to the field of surfactantcompounds and methods of making the same. In particular, the presentdisclosure is related to a new class of compounds that comprise twoidentical hydrophilic cationic or anionic groups and one hydrophobicgroup. The disclosed compounds share some structural features withconventional or Gemini surfactants but are structurally distinguishablefrom existing surfactants. The disclosed compounds are useful as asurfactant alone or together with other conventional or Geminisurfactant(s) in various applications.

BACKGROUND OF THE INVENTION

A surfactant compound usually contains a hydrophilic group andhydrophobic group. Because of its unique structure, a surfactant hasvarious applications in different fields. As the understanding of therelationship between a surfactant compound's structure and its functionand mode of operation improves, the need for surfactant compounds havingnew or improved properties, such as surface tension properties, isincreasing.

Although structures of surfactants are diverse and numerous, theexisting surfactants can be classified into two broad categories; one ofconventional surfactants and another of Gemini surfactants.

A conventional surfactant usually has a hydrophobic group and ahydrophilic group. Depending on the characteristics of the hydrophilicgroup, a conventional surfactant can be one of nonionic, anionic,cationic, amphoteric, or zwitterionic surfactants.

A Gemini surfactant, on the other hand, has two hydrophobic groups andtwo hydrophilic groups. Gemini surfactants can be further dividedsimilar subcategories based on the characteristics of the hydrophobicgroup(s), in an analogous manner as used for classifying a conventionalsurfactant.

Accordingly, it is an objective to develop novel surfactant compoundshaving properties distinguishable from conventional and/or Geminisurfactants. In both conventional and Gemini surfactants, the ratio ofhydrophilic group to hydrophobic group is 1:1, while the disclosedcompounds have a ratio of hydrophilic group to hydrophobic group of 2:1.This difference in the ratio of hydrophilic group to hydrophobic groupprovides for unique applications of the disclosed compounds, not only assurfactants, but also as antimicrobials, sanitizers, fabric softeners,antistatic agents, corrosion inhibitors, foaming agents, floatationcollectors, dispersants, surfactants assisted enhanced oil recovery(EOR), cleaners, etc.

It is a further objective of the disclosure to develop a method to makethe novel compounds efficiently and effectively.

It is a further objective of the disclosure to use the novel compoundsin an article, product, and/or composition.

These and other objects, advantages and features of the presentdisclosure will become apparent from the following specification takenin conjunction with the claims set forth herein.

BRIEF SUMMARY OF THE INVENTION

Disclosed herein are novel compounds, including surfactant compounds,compositions comprising the disclosed compounds and methods of makingthe disclosed compounds. More particularly, disclosed herein are thecompounds comprising two identical hydrophilic groups and a singlehydrophobic group. In a disclosed compound, each hydrophilic groupincludes or ends in a quaternary amine or a negatively charged species,and the hydrophobic group includes a long hydrophobic chain. Thedisclosed compounds are different from conventional or Geminisurfactants, because the ratio of hydrophilic groups to hydrophobicgroup in the closed compounds is 2:1, while in conventional or Geminisurfactants the ratio is 1:1. This difference in structure providesunique applications for the disclosed compounds, not only assurfactants, but also for other purposes, such as antimicrobialsanitizers, fabric softeners, antistatic agents, corrosion inhibitors,foaming agents, floatation collectors, dispersants, surfactants assistedenhanced oil recovery (EOR), cleaners, etc.

In one aspect, a compound according to Formula I is provided:

wherein

X is NH, or O;

R¹¹ is R¹ or R¹—Z—(CH₂)_(m)—;

R¹ is an unsubstituted or substituted, linear or branched C₁-C₃₀ alkyl,cyclic alkyl, alkenyl, or alkynyl group;

Z is NH or O;

R² is H, CH₃, or an unsubstituted, linear or branched C₁-C₁₀ alkyl,alkenyl, or alkynyl group;

m is an integer of 1 to 4;

R³ is absent or an unsubstituted, linear C₁-C₃₀ alkylene group;

Y is —NR₄R₅R₆ ⁽⁺⁾ or a salt thereof; and

R⁴, R⁵, and R⁶ are independently C₁-C₁₀ alkyl group.

In other aspect, disclosed herein is a method to synthesize thedisclosed compounds. The method comprises contacting a primary aminewith an activated olefin containing at least one cationic group togenerate any compound disclosed herein; wherein the primary amine isR¹¹—NH₂, R¹¹ is R¹ or R¹—Z—(CH₂)_(m)—; the activated olefin is

X is NH, or O;

R¹¹ is R¹ or R¹—Z—(CH₂)_(m)—;

R¹ is an unsubstituted or substituted, linear or branched C₁-C₃₀ alkyl,cyclic alkyl, alkenyl, or alkynyl group;

Z is NH or O;

R² is H, CH₃, or an unsubstituted, linear or branched C₂-C₁₀ alkyl,alkenyl, or alkynyl group;

m is an integer of 1 to 4;

R³ is absent or an unsubstituted, linear C₁-C₃₀ alkylene group;

Y is —NR₄R₅R₆ ⁽⁺⁾ or a salt thereof; and

R⁴, R⁵, and R⁶ are independently C₁-C₁₀ alkyl group.

In yet another aspect, provided herein is an article, product, orcomposition that comprises one or more compounds disclosed herein.

In yet another aspect, provided herein is a composition comprising oneor more compounds disclosed herein.

The forgoing summary is illustrative only and is not intended to be inany way limiting. In addition to the illustrative aspects, embodimentsand features described above, further aspects, embodiments, and featuresof the present technology will become apparent to those skilled in theart from the following drawings and the detailed description, whichshows and describes illustrative embodiments of the present technology.Accordingly, the figures and detailed description are also to beregarded as illustrative in nature and not in any way limiting.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1A, FIG. 1B, and FIG. 1C show a representation of an exemplarycompound of the disclosure (FIG. 1C), together with comparativerepresentations for a conventional surfactant (FIG. 1A) and Geminisurfactant (FIG. 1B).

FIG. 2 shows a generic reaction scheme between a primary amine (Michaeldonor) and activated olefin (Michael acceptor) including a cationicgroup (Michael acceptor).

Various embodiments of the present invention will be described in detailwith reference to the drawings, wherein like reference numeralsrepresent like parts throughout the several views. Reference to variousembodiments does not limit the scope of the invention. Figuresrepresented herein are not limitations to the various embodimentsaccording to the invention and are presented for exemplary illustrationof the invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Disclosed herein are novel compounds and methods of making these novelcompounds or surfactant compositions. More particularly, compoundscomprising two identical hydrophilic groups and one hydrophobic group inthe molecule, and methods of synthesizing such surfactants aredisclosed. For example, each hydrophilic group includes or ends with aquaternary amine and the hydrophobic group includes a long aliphaticchain.

The embodiments of this invention are not limited to particularcompositions and methods of use which can vary and are understood byskilled artisans. It is further to be understood that all terminologyused herein is for the purpose of describing particular embodiments onlyand is not intended to be limiting in any manner or scope. For example,as used in this specification and the appended claims, the singularforms “a,” “an” and “the” can include plural referents unless thecontent clearly indicates otherwise. Further, all units, prefixes, andsymbols may be denoted in its SI accepted form.

Numeric ranges recited within the specification are inclusive of thenumbers within the defined range. Throughout this disclosure, variousaspects of this invention are presented in a range format. Thedescription in range format is merely for convenience and brevity andshould not be construed as an inflexible limitation on the scope of theinvention. Accordingly, the description of a range should be consideredto have specifically disclosed all the possible sub-ranges as well asindividual numerical values within that range (e.g. 1 to 5 includes 1,1.5, 2, 2.75, 3, 3.80, 4, and 5).

So that the present invention may be more readily understood, certainterms are first defined. Unless defined otherwise, all technical andscientific terms used herein have the same meaning as commonlyunderstood by one of ordinary skill in the art to which embodiments ofthe invention pertain. Many methods and materials similar, modified, orequivalent to those described herein can be used in the practice of theembodiments of the present invention without undue experimentation, thepreferred materials and methods are described herein. In describing andclaiming the embodiments of the present invention, the followingterminology will be used in accordance with the definitions set outbelow.

The term “about,” as used herein, refers to variation in the numericalquantity that can occur, for example, through typical measuring andliquid handling procedures used for making concentrates or use solutionsin the real world; through error in these procedures; throughdifferences in the manufacture, source, or purity of the ingredientsused to make the compositions or carry out the methods; and the like.The term “about” also encompasses amounts that differ due to novelequilibrium conditions for a composition resulting from a particularinitial mixture. Whether or not modified by the term “about”, the claimsinclude equivalents to the quantities.

As used herein, “substituted” refers to an organic group as definedbelow (e.g., an alkyl group) in which one or more bonds to a hydrogenatom contained therein are replaced by a bond to non-hydrogen ornon-carbon atoms. Substituted groups also include groups in which one ormore bonds to carbon(s) or hydrogen(s) atom replaced by one or morebonds, including double or triple bonds, to a heteroatom. Thus, asubstituted group is substituted with one or more substituents, unlessotherwise specified. A substituted group can be substituted with 1, 2,3, 4, 5, or 6 substituents.

Substituted ring groups include rings and ring systems in which a bondto a hydrogen atom is replaced with a bond to a carbon atom. Therefore,substituted cycloalkyl, aryl, heterocyclyl, and heteroaryl groups mayalso be substituted with substituted or unsubstituted alkyl, alkenyl,and alkynyl groups are defined herein.

As used herein, the term “alkyl” or “alkyl groups” refers to saturatedhydrocarbons having one or more carbon atoms, including straight-chainalkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, etc.), cyclic alkyl groups (or “cycloalkyl” or“alicyclic” or “carbocyclic” groups) (e.g., cyclopropyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched-chain alkyl groups(e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc.), andalkyl-substituted alkyl groups (e.g., alkyl-substituted cycloalkylgroups and cycloalkyl-substituted alkyl groups).

Unless otherwise specified, the term “alkyl” includes both“unsubstituted alkyls” and “substituted alkyls.” As used herein, theterm “substituted alkyls” refers to alkyl groups having substituentsreplacing one or more hydrogens on one or more carbons of thehydrocarbon backbone. Such substituents may include, for example,alkenyl, alkynyl, halogeno, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy,alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate,alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl,phosphate, phosphonato, phosphinato, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino),acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyland ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate,sulfates, alkylsulfinyl, sulfonates, sulfamoyl, sulfonamido, nitro,trifluoromethyl, cyano, azido, heterocyclic, alkylaryl, or aromatic(including heteroaromatic) groups.

In some embodiments, substituted alkyls can include a heterocyclicgroup. As used herein, the term “heterocyclic group” includes closedring structures analogous to carbocyclic groups in which one or more ofthe carbon atoms in the ring is an element other than carbon, forexample, nitrogen, sulfur or oxygen. Heterocyclic groups may besaturated or unsaturated. Exemplary heterocyclic groups include, but arenot limited to, aziridine, ethylene oxide (epoxides, oxiranes), thiirane(episulfides), dioxirane, azetidine, oxetane, thietane, dioxetane,dithietane, dithiete, azolidine, pyrrolidine, pyrroline, oxolane,dihydrofuran, and furan.

Alkenyl groups or alkenes are straight chain, branched, or cyclic alkylgroups having two to about 30 carbon atoms, and further including atleast one double bond. In some embodiments, an alkenyl group has from 2to about 30 carbon atoms, or typically, from 2 to 10 carbon atoms.Alkenyl groups may be substituted or unsubstituted. For a double bond inan alkenyl group, the configuration for the double bond can be a transor cis configuration. Alkenyl groups may be substituted similarly toalkyl groups.

Alkynyl groups are straight chain, branched, or cyclic alkyl groupshaving two to about 30 carbon atoms, and further including at least onetriple bond. In some embodiments, an alkynyl group has from 2 to about30 carbon atoms, or typically, from 2 to 10 carbon atoms. Alkynyl groupsmay be substituted or unsubstituted. Alkynyl groups may be substitutedsimilarly to alkyl or alkenyl groups.

As used herein, the terms “alkylene”, cycloalkylene”, “alkynylides”, and“alkenylene”, alone or as part of another substituent, refer to adivalent radical derived from an alkyl, cycloalkyl, or alkenyl group,respectively, as exemplified by —CH₂CH₂CH₂—. For alkylene,cycloalkylene, alkynylene, and alkenylene groups, no orientation of thelinking group is implied.

The term “ester” as used herein refers to —R³⁰COOR³¹ R group. R³⁰ isabsent, a substituted or unsubstituted alkylene, cycloalkylene,alkenylene, alkynylene, arylene, aralkylene, heterocyclylalkylene, orheterocyclylene group as defined herein. R³¹ is a substituted orunsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl,heterocyclylalkyl, or heterocyclyl group as defined herein.

The term “amine” (or “amino”) as used herein refers to —R³²NR³³R³⁴groups. R³² is absent, a substituted or unsubstituted alkylene,cycloalkylene, alkenylene, alkynylene, arylene, aralkylene,heterocyclylalkylene, or heterocyclylene group as defined herein. R³³and R³⁴ are independently hydrogen, or a substituted or unsubstitutedalkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclylalkyl,or heterocyclyl group as defined herein.

The term “amine” as used herein also refers to an independent compound.When an amine is a compound, it can be represented by a formula ofR^(32′)NR^(33′)R^(34′) groups, wherein R^(32′), R^(33′), and R³⁴ areindependently hydrogen, or a substituted or unsubstituted alkyl,cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclylalkyl, orheterocyclyl group as defined herein.

The term “alcohol” as used herein refers to —R³⁵OH groups. R³⁵ isabsent, a substituted or unsubstituted alkylene, cycloalkylene,alkenylene, alkynylene, arylene, aralkylene, heterocyclylalkylene, orheterocyclylene group as defined herein.

The term “carboxylic acid” as used herein refers to —R³⁶COOH groups. R³⁶is absent, a substituted or unsubstituted alkylene, cycloalkylene,alkenylene, alkynylene, arylene, aralkylene, heterocyclylalkylene, orheterocyclylene group as defined herein.

The term “ether” as used herein refers to —R³⁷OR³⁸ groups. R³⁷ isabsent, a substituted or unsubstituted alkylene, cycloalkylene,alkenylene, alkynylene, arylene, aralkylene, heterocyclylalkylene, orheterocyclylene group as defined herein. R³⁸ is a substituted orunsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl,heterocyclylalkyl, or heterocyclyl group as defined herein.

The term “solvent” as used herein refers to any inorganic or organicsolvent. Solvents are useful in the disclosed method or article,product, or composition as reaction solvent or carrier solvent. Suitablesolvents include, but are not limited to, oxygenated solvents such aslower alkanols, lower alkyl ethers, glycols, aryl glycol ethers andlower alkyl glycol ethers. Examples of other solvents include, but arenot limited to, methanol, ethanol, propanol, isopropanol and butanol,isobutanol, ethylene glycol, diethylene glycol, triethylene glycol,propylene glycol, dipropylene glycol, hexylene glycol, mixedethylene-propylene glycol ethers, ethylene glycol phenyl ether, andpropylene glycol phenyl ether. Water is a solvent too. The solvent usedherein can be of a single solvent or a mixture of many differentsolvents.

Glycol ethers include, but are not limited to, diethylene glycol n-butylether, diethylene glycol n-propyl ether, diethylene glycol ethyl ether,diethylene glycol methyl ether, diethylene glycol t-butyl ether,dipropylene glycol n-butyl ether, dipropylene glycol methyl ether,dipropylene glycol ethyl ether, dipropylene glycol propyl ether,dipropylene glycol tert-butyl ether, ethylene glycol butyl ether,ethylene glycol propyl ether, ethylene glycol ethyl ether, ethyleneglycol methyl ether, ethylene glycol methyl ether acetate, propyleneglycol n-butyl ether, propylene glycol ethyl ether, propylene glycolmethyl ether, propylene glycol n-propyl ether, tripropylene glycolmethyl ether and tripropylene glycol n-butyl ether, ethylene glycolphenyl ether, propylene glycol phenyl ether, and the like, or mixturesthereof.

In one aspect, disclosed herein is a compound according to Formula I

wherein

X is NH, or O;

R¹¹ is R¹ or R¹—Z—(CH₂)_(m)—;

R¹ is an unsubstituted or substituted, linear or branched C₁-C₃₀ alkyl,cyclic alkyl, alkenyl, or alkynyl group;

Z is NH or O;

R² is H, CH₃, or an unsubstituted, linear or branched C₂-C₁₀ alkyl,alkenyl, or alkynyl group;

m is an integer of 1 to 4;

R³ is absent or an unsubstituted, linear C₁-C₃₀ alkylene group;

Y is —NR₄R₅R₆ ⁽⁺⁾ or a salt thereof; and

R⁴, R⁵, and R⁶ are independently C₁-C₁₀ alkyl group.

In some embodiments of the disclosed compounds herein, X is NH. In someother embodiments, X is O.

In some embodiments, R¹¹ is R¹. In some other embodiments, R¹¹ isR¹—Z—(CH₂)_(m)—.In some embodiments, R¹¹ is R¹—Z—(CH₂)_(m)—, and Z isNH. In some other embodiments, R¹¹ is R¹—Z—(CH₂)_(m)—, and Z is O. Inyet some other embodiments, R¹¹ is R¹—Z—(CH₂)_(m)—, Z isNH, m is 2.

In some embodiments, R² is H. In some embodiments, R² is CH₃. In yetsome other embodiments, R² is CH₃CH₃, CH₂CH₂CH₃, or CH(CH₃)₂.

In some embodiments, Y is —NR₄R₅R₆ ⁽⁺⁾. In some other embodiments, Y is—NR₄R₅R₆ ⁽⁺⁾, and R⁴, R⁵, and R⁶ are independently CH₃. In yet someother embodiments, Y is —NR₄R₅R₆ ⁽⁺⁾, and R⁴ and R⁵, independently CH₃,and R⁶ is a C₆-C₁₂ aromatic alkyl. In some other embodiments, Y is—NR₄R₅R₆ ⁽⁺⁾, and R⁴ and R⁵, independently CH₃, and R⁶ is —CH₂—C₆H₅.

In some embodiments, Y is —NR₄R₅R₆ ⁽⁺⁾ and the counter ion for Y is anynegative charged ion or species. In some other embodiments, the counterion for Y is chloride, bromide, fluoride, iodide, acetate, aluminate,cyanate, cyanide, dihydrogen phosphate, dihydrogen phosphite, formate,carbonate, hydrogen carbonate, hydrogen oxalate, hydrogen sulfate,hydroxide, nitrate, nitrite, thiocyanate, or a combination thereof.

In some embodiments, R³ is CH₂. In some other embodiments, R³ is CH₂CH₂.In other embodiments, R³ is C(CH₃)₂. In yet some other embodiments, R³is an unsubstituted, linear, and saturated C₂-C₁₀ alkylene group. Insome embodiments, R³ is an unsubstituted, linear, and unsaturated C₂-C₁₀alkylene group.

In some embodiments, R¹ is a linear C₁-C₃₀ alkyl, alkenyl, or alkynylgroup. In some other embodiments, R¹ is a branched C₁-C₃₀ alkyl,alkenyl, or alkynyl group. In yet some other embodiments, R¹ is a linearand saturated C₅-C₃₀ alkyl group. In some other embodiments, R¹ is abranched and saturated C₅-C₃₀ alkyl group.

In some embodiments, R¹ is a linear C₁-C₃₀ alkenyl group with one ormore double bonds. In some other embodiments, wherein R¹ is a branchedC₁-C₃₀ alkenyl group with one or more double bonds.

In some embodiments, R¹ is a linear C₁-C₃₀ alkynyl group with one ormore triple bonds. In some other embodiments, R¹ is a branched C₁-C₃₀alkynyl group with one or more triple bonds.

In some embodiments, R¹¹ is a linear and saturated C₂-C₂₀ alkyl group.In some other embodiments, R¹¹ is a trans C₂-C₂₀ alkenyl group with atleast one double bond. In some other embodiments, R¹¹ is a C₂-C₂₀alkenyl group with at least one double bond of trans configuration. Insome embodiments, R¹¹ is a cis C₂-C₂₀ alkenyl group with at least onedouble bond. In some other embodiments, R¹¹ is a C₂-C₂₀ alkenyl groupwith at least one double bond of cis configuration.

In some embodiments, R¹¹ is R¹—NH—CH₂CH₂CH₂ group and R¹ is a linear andsaturated C₂-C₂₀ alkyl, a trans alkenyl, or a cis alkenyl group.

In some other embodiments, R² is H, X is NH, R³ is CH₂CH₂, Y isCH₂—N⁺(CH₃)₃Cl⁻.

In another aspect, disclosed herein is a compound according to FormulaII or Formula III

wherein X is NH, or O; R¹¹ is R¹ or R¹—Z—(CH₂)_(m)—; R¹ is anunsubstituted or substituted, linear or branched C₁-C₃₀ alkyl, cyclicalkyl, alkenyl, or alkynyl group; Z is NH or O; R² is H, CH₃, or anunsubstituted, linear or branched C₁-C₁₀ alkyl, alkenyl, or alkynylgroup; R^(2′) is H, CH_(3,) or an unsubstituted or substituted, linearor branched C₁-C₁₀ alkyl, alkenyl, alkynyl group, —COOH, —CH₂COOH, Y′,or —(CH₂)_(m)—Y′; m is an integer of 1 to 4; R³ is absent or anunsubstituted, linear C₁-C₃₀ alkylene group; Y′ is —COOH, —PO₃H,—OPO₃H,—SO₃H, —OSO₃H or salt thereof.

In some embodiments, Y′ is —COOH or salt thereof. In some embodiments,Y′ is —PO₃H, —OPO₃H, or salt thereof. In some other embodiments, Y′ is—SO₃H, —OSO₃H, or salt thereof.

In some embodiments of the disclosed compounds herein, X is NH. In someother embodiments, X is O.

In some embodiments, R¹¹ is R¹. In some other embodiments, R¹¹ isR¹—Z—(CH₂)_(m)—. In some embodiments, R¹¹ is R¹—Z—(CH₂)_(m)—, and Z isNH. In some other embodiments, R¹¹ is R¹—Z—(CH₂)_(m)—, and Z is O. Inyet some other embodiments, R¹¹ is R¹—Z—(CH₂)_(m)—, Z is NH, m is 2.

In some embodiments, R² is H. In some embodiments, R² is CH₃. In yetsome other embodiments, R² is CH₃CH₃, CH₂CH₂CH₃, or CH(CH₃)₂.

In some embodiments, R^(2′) is H. In some embodiments, R^(2′) is CH₃. Inyet some other embodiments, R^(2′) is CH₃CH₃, CH₂CH₂CH₃, or CH(CH₃)₂. Insome other embodiments, R^(2′) is —COOH. In some other embodiments,R^(2′) is —CH₂COOH.

In some embodiments, R³ is CH₂. In some other embodiments, R³ is CH₂CH₂.In other embodiments, R³ is C(CH₃)₂. In yet some other embodiments, R³is an unsubstituted, linear, and saturated C₂-C₁₀ alkylene group. Insome embodiments, R³ is an unsubstituted, linear, and unsaturated C₂-C₁₀alkylene group.

In some embodiments, R¹ is a linear C₁-C₃₀ alkyl, alkenyl, or alkynylgroup. In some other embodiments, R¹ is a branched C₁-C₃₀ alkyl,alkenyl, or alkynyl group. In yet some other embodiments, R¹ is a linearand saturated C₅-C₃₀ alkyl group. In some other embodiments, R¹ is abranched and saturated C₅-C₃₀ alkyl group.

In some embodiments, R¹ is a linear C₁-C₃₀ alkenyl group with one ormore double bonds. In some other embodiments, wherein R¹ is a branchedC₁-C₃₀ alkenyl group with one or more double bonds.

In some embodiments, R¹ is a linear C₁-C₃₀ alkynyl group with one ormore triple bonds. In some other embodiments, R¹ is a branched C₁-C₃₀alkynyl group with one or more triple bonds.

In some embodiments, R¹¹ is a linear and saturated C₂-C₂₀ alkyl group.In some other embodiments, R¹¹ is a trans C₂-C₂₀ alkenyl group with atleast one double bond. In some other embodiments, R¹¹ is a C₂-C₂₀alkenyl group with at least one double bond of trans configuration. Insome embodiments, R¹¹ is a cis C₂-C₂₀ alkenyl group with at least onedouble bond. In some other embodiments, R¹¹ is a C₂-C₂₀ alkenyl groupwith at least one double bond of cis configuration.

In some embodiments, R¹¹ is R¹—NH—CH₂CH₂CH₂ group and R¹ is a linear andsaturated C₁-C₂₀ alkyl, a trans alkenyl, or a cis alkenyl group.

In some other embodiments, R² is H, X is NH, R³ is CH₂CH₂, Y′ is —COOHor —PO₃H. In some embodiments, the compound is one by Formula II. Insome other embodiments, the compound is one by Formula III.

In some embodiments, the compound is one with formula III, R^(2′) is H,X is NH, Y′ is —COOH or —PO₃H. In some other embodiments, the compoundis one with formula III, R^(2′) is —CH₃, X is NH, Y′ is —COOH or —PO₃H.In yet some other embodiments, the compound is one with formula III,R^(2′) is Y′ or —CH₂Y′, X is NH, Y′ is —COOH or —PO₃H.

In yet some other embodiments, when the compound is one with formula IIIand the Y′ group is negatively charged, the counter positive ions forthe negative charges include, but are not limited to, alkali metal ions,Li⁺, Na⁺, K⁺, NH₄ ⁺, a quaternary ammonium ion, etc.

Without being limited to a particular mechanism of action or definitionof structure and function of the compounds, the compounds disclosedherein have two hydrophilic groups associated with one hydrophobicgroup. Accordingly, the compounds disclosed herein have a ratio ofhydrophilic groups to hydrophobic group of 2:1 as compared to both aconventional surfactant and Gemini surfactant, which exhibit a 1:1ratio. FIG. 1A, FIG. 1B, and FIG. 1C shows a representation of anexemplary compound disclosed herein (FIG. 1C), together with ones for aconventional (FIG. 1A) and Gemini surfactant (FIG. 1B). Due to thehigher ratio of hydrophilic groups to hydrophobic group, the disclosedcompounds are particularly well suited for use as antimicrobialsanitizers, fabric softeners, antistatic agents, corrosion inhibitors,foaming agents, floatation collectors, dispersants, surfactants assistedenhanced oil recovery (EOR), cleaners, etc.

In this disclosure, the term “hydrophobic group” can be usedinterchangeable with the term “hydrophobic tail or head.” Similarly, theterm “hydrophilic group” can be used interchangeably with the term“polar head or tail”, or “hydrophilic group”, or “polar group.” The term“a molecule” can also be used interchangeably with the term “acompound.”

Methods of Making

In another aspect, disclosed herein is a method to synthesize thecompounds disclosed herein. The disclosed method comprises contacting aprimary amine (Michael donor) with an activated olefin containing ahydrophilic group (Michael acceptor) at a temperature of from about −20°C. to about 200° C., in some embodiments, for from about 10 minutes toabout 48 hours, to generate the compounds disclosed herein. The reactionleading to the compounds disclosed herein is aza-Michael additionbetween a primary amine (Michael donor) and an activated olefincontaining a hydrophilic group (Michael acceptor).

An aliphatic amine group may undergo an aza-Michael Addition reactionwhen in contact with an unsaturated hydrocarbon moiety (e.g.,carbon-carbon double bond) that is in proximity of an electronwithdrawing group such as carbonyl, cyano, or nitro group. Specifically,the Michael addition is a reaction between nucleophiles and activatedolefin and alkyne functionalities, wherein the nucleophile adds across acarbon-carbon multiple bond that is adjacent to an electron withdrawingand resonance stabilizing activating group, such as a carbonyl group.The Michael addition nucleophile is known as the “Michael donor”, theactivated electrophilic olefin is known as the “Michael acceptor”, andreaction product of the two components is known as the “Michael adduct.”Examples of Michael donors include, but are not restricted to, amines,thiols, phosphines, carbanions, and alkoxides. Examples of Michaelacceptors include, but are not restricted to, acrylate esters, alkylmethacrylates, acrylonitrile, acrylamides, maleimides, cyanoacrylatesand vinyl sulfones, vinyl ketones, nitro ethylenes, α, β-unsaturatedaldehydes, vinyl phosphonates, acrylonitrile, vinyl pyridines, azocompounds, beta-keto acetylenes and acetylene esters.

As used herein, an “activated olefin” refers to a substituted alkene inwhich at least one of the double-bond carbon has a conjugated electronwithdrawing group. Examples of activated olefins include, but notlimited to, α, β-unsaturated carbonyl compounds (such asCH₂═CHCO—NH—CH₃, alkyl-CH═CH—CO-alkyl, CH₂═CH₂C(O)—O—CH₃), CH₂═CH—COOH,CH₂═CH(CH₃)—COOH, CH₂═CH—SO₃H, and like.

As used herein, “contacting” is referred to any way to bring the primaryamine (Michael donor) and the activated olefin containing at least onecationic or anionic group (Michael acceptor) together as one skilled inthe art would do to conduct a chemical reaction in a controlled andpractical manner. For example, in some embodiments, the primary amine ora solution comprising the primary amine can be added into a container orvessel containing the activated olefin or a solution comprising theactivated olefin, in batches or drops. In some other embodiments, theactivated olefin or a solution comprising the activated olefin can beadded into a container or vessel containing the primary amine or asolution comprising the primary amine, in batches or drops. In yet someother embodiments, both the activated olefin or a solution comprisingthe activated olefin and the primary amine or a solution comprising theprimary amine are added to a container or vessel in batches or drops,simultaneously, sequentially, or alternatively.

The chemical reaction used to synthesize the disclosed compounds isAza-Michael addition reaction. It was found that the Aza-Michaeladdition can be used to synthesize the disclosed compounds under mildconditions and a high yield for the disclosed compounds in a reasonablereaction time.

Aza-Michael addition reaction can be catalyzed by a strong acid or base.In some cases, some ionic liquids can function both as reaction mediaand catalyst. The preferred catalyst for the Aza-Michael additionreaction to synthesize the disclosed compounds is a base. The basecatalyst can be any or a combination of an alkalinity source or primaryalkalinity source. Exemplary base catalyst can be an alkali metal,hydroxide, alkali metal carbonate, alkali metal silicate, alkali metalsilicate, or amine. Exemplary base catalyst can be hydroxide and amines.Because the reaction to synthesize the disclosed compounds uses aprimary amine, the primary amine itself can function as a catalyst forthe reaction. In such embodiments, no additional catalyst is necessary,or an additional catalyst is optional. Other preferred catalysts includeamidine and guanidine bases.

The use of solvent and/or diluent for the reaction is optional. Whenemployed, a wide range of non-acidic solvents are suitable, such as, forexample, water, ethers (e.g., tetrahydrofuran (THF)), aromatichydrocarbons (e.g., toluene and xylene), alcohols (e.g., n-butanol),esters (e.g., ethyl 3-ethoxypropionate), and the like. A wide range ofsolvents can be used for the reaction because the synthesis process isrelatively insensitive to solvent. When solvent (or diluent) isemployed, loading levels can range from about 0 wt-% up to about 80 wt-%and higher. The solvent loading level can be about 0 wt-%, from about 1wt-% to about 10 wt-%, from about 10 wt-% to about 20 wt-%, from about20 wt-% to about 30 wt-%, from about 30 wt-% to about 40 wt-%, fromabout 40 wt-% to about 50 wt-%, from about 50 wt-% to about 60 wt-%,from about 60 wt-% to about 70 wt-%, from about 70 wt-% to about 80wt-%, from about 1 wt-% to about 20 wt-%, from about 20 wt-% to about 40wt-%, from about 40 wt-% to about 60 wt-%, from about 60 wt-% to about80 wt-%, from about 40 wt-% to about 70 wt-%, about 5 wt-%, about 15wt-%, about 25 wt-%, about 35 wt-%, about 45 wt-%, about 55 wt-%, about65 wt-%, about 75 wt-%, or any value there between of the final reactionmixture.

Generally, the contacting step of the method can be carried out at atemperature over a wide range of temperatures. The contacting, orreaction temperature can range from about −20° C. to about 200° C., fromabout 0° C. to about 150° C., more preferably from about 50° C. to about80° C. The contacting temperature can be from about 10° C. to about 140°C., about 20° C. to about 130° C., about 30° C. to about 120° C., about40° C. to about 110° C., about 50° C. to about 100° C., about 60° C. toabout 90° C., about 70° C. to about 80° C., about 0° C. to about 20° C.,about 20° C. to about 40° C., about 40° C. to about 60° C., about 60° C.to about 80° C., about 80° C. to about 100° C., about 100° C. to about120° C., about 120° C. to about 150° C., about 5° C., about 25° C.,about 45° C., about 65° C., about 85° C., about 105° C., about 125° C.,about 145° C., or any value there between. The reaction temperature canbe about the same from starting of the reaction to end of the reactionand can be changed from one temperature to another while the reaction isgoing on.

The contacting or reaction time for the synthesis of the compoundsdisclosed herein can vary widely, depending on such factors as thereaction temperature, the efficacy and amount of the catalyst, thepresence or absence of diluent (solvent), and the like. The preferredreaction time can be from about 10 minutes to about 48 hours, from about0.5 hours to about 48 hours, from about 1 hour to 40 hours, from about 2hours to 38 hours, from about 4 hours to about 36 hours, from 6 hours toabout 34 hours, from about 8 hours to about 32 hours, from about 10hours to about 30 hours, from about 12 hours to about 28 hours, fromabout 14 hours to 26 hours, from about 16 hours to 24 hours, from about18 hours to 20 hours, from about 1 hour to 8 hours, from 8 hours to 16hours, from 8 hours to about 24 hours, about 2 hours, about 4 hours,about 6 hours, about 8 hours, about 10 hours, about 14 hours, about 16hours, about 18 hours, about 24 hours, about 30 hours, about 36 hours,or any values there between.

The reaction for the synthesis of the compounds disclosed herein can goto completion when one mole of the primary amine and at least two molesof the activated olefin, are mixed together for a sufficient of time ata temperature described above. Typically, if the reaction is carried outat a room temperature, the reaction can have a product yield of morethan 98%.

In some embodiments of the disclosed methods, the primary amine isR¹¹—NH₂, R¹¹ is R¹ or R¹—Z—(CH₂)_(m)—; the activated olefin is

X is NH, or O;

R¹¹ is R¹ or R¹—Z—(CH₂)_(m)—;

R¹ is an unsubstituted or substituted, linear or branched C₁-C₃₀ alkyl,cyclic alkyl, alkenyl, or alkynyl group;

Z is NH or O;

R² is H, CH₃, or an unsubstituted, linear or branched C₁-C₁₀ alkyl,alkenyl, or alkynyl group;

m is an integer of 1 to 4;

R³ is absent or an unsubstituted, linear C₁-C₃₀ alkylene group;

Y is —NR₄R₅R₆ ⁽⁺⁾ or a salt thereof; and

R⁴, R⁵, and R⁶ are independently C₁-C₁₀ alkyl group.

In some embodiments, the activated olefin activated olefin is(3-Acrylamidopropyl)trimethylammonium chloride (APTAC),[3-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC),2-(acryloyloxy)-N,N,N-trimethylethanaminium chloride (DMAEA-MCQ),N,N-dimethylaminoethyl acrylate benzyl chloride quaternary salt(DMAEA-BCQ), 2-(methacryloyloxy)-N,N,N-trimethylethan-1-aminium methylsulfate (DMAEA-MSQ), or mixture thereof.

In some embodiments of the disclosed methods, the primary amine isR¹¹—NH₂, R¹¹ is R¹ or R¹—Z—(CH₂)_(m)—; the activated olefin is

X is NH, or O;

R¹¹ is R¹ or R¹—Z—(CH₂)_(m)—;

R¹ is an unsubstituted or substituted, linear or branched C₁-C₃₀ alkyl,cyclic alkyl, alkenyl, or alkynyl group;

Z is NH or O;

R² is H, CH₃, or an unsubstituted, linear or branched C₁-C₁₀ alkyl,alkenyl, or alkynyl group;

R²′ is H, CH₃, or an unsubstituted or substituted, linear or branchedC₁-C₁₀ alkyl, alkenyl, alkynyl group, —COOH, —CH₂COOH, Y′, or—(CH₂)_(m)—Y′;

m is an integer of 1 to 4;

R³ is absent or an unsubstituted, linear C₁-C₃₀ alkylene group; and

Y′ is —COOH, —PO₃H, —SO₃H, —OSO₃H, —OPO₃H, or a salt thereof.

In some embodiments, the activated olefin is acrylic acid, methacrylicacid, itaconic acid, maleic acid, vinylsulfonic acid, vinylphosphonicacid, or mixture thereof.

In some other embodiments, the activated olefin is2-acrylamido-2-methylpropane sulfonic acid (AMPS),3-(allyloxy)-2-hydroxypropane-1-sulfonate, or mixture thereof.

In yet some other embodiments, when the activated olefin containsanionic group that can bear negative charge at an alkaline pH, thecounter positive ions for the negative charges include, but are notlimited to, alkali metal ions, Li⁺, Na⁺, K⁺, NH₄ ⁺, a quaternaryammonium ion, etc.

In some embodiments of the disclosed methods, the contacting step isdone in the presence of a reaction solvent. The reaction solvent can beany inorganic or organic solvent commonly used in chemical synthesis.The reaction solvent used in the disclosed method can be introduced intothe reaction between the primary amine and the activated olefinincluding a cationic or anionic group by any way known by one skilled inthe art. For example, the solvent can be added into the container orvessel for reaction before, at the same, with one or both reactants, orafter the primary amine, the activated olefin, or both are added.

In some embodiments, the reaction solvent is water, methanol, ethanol,propanol, glycol, PEG, or a mixture thereof In some other embodiments,the reaction solvent is water.

In some other embodiments of the disclosed methods, the contacting stepis done in the presence of a catalyst, base, or acid. The catalyst,base, or acid can be introduced into the reaction between the primaryamine and activated olefin by any way known by one skilled in the art.

In some embodiments, the contacting step is done without the presence ofany additional base. In some other embodiments, the contacting step isdone in the presence of an alkalinity source. In some other embodiments,the contacting step is done in the presence of an organic base, such asalkanolamines. In yet some other embodiments, the contacting step isdone in the presence of an alkali metal hydroxide, carbonate,imidazole/pyridine based base, or combination thereof, such as NaOH,Na₂CO₃, aminoethyl pyridine, aminopropyl imidazole, or a combinationthereof. In some other embodiments, the contacting step is done with thepresence of benzyltrimethylammonium hydroxide. In some embodiments, thecatalyst base is an amidine or guanidine base, or mixtures thereof. Insome other embodiments, the catalyst is a ionic liquid, such as1,8-diazabicyclo[5.4.0]-undec-7-en-8-ium acetate, for the reaction undera solvent free condition at room temperatures.

In yet some other embodiments of the disclosed methods, the contactingstep is done in the presence of an acid. In some other embodiments, thecontacting step is done in the presence of a catalyst. The catalyst canany one or more of the catalysts known for the Michael addition reactionby one skilled in the art.

In yet some other embodiments of the disclosed methods, the contactingstep is done free of a catalyst, base, or acid. In some otherembodiments, the contacting step is done free of an alkali metalhydroxide, carbonate, silicate, metasilicate, imidazole/pyridine-basedbase, or all thereof. In some embodiments, the contact step is done freeof a base.

In yet another aspect, disclosed herein is an article, product, orcomposition comprising one or more compounds disclosed here or producedby the methods disclosed herein.

In some embodiments, the article, product or composition furthercomprises a carrier solvent or a carrier. As used herein, a “carriersolvent” or carrier is a solvent or solvent system in which thedisclosed compound can be distributed evenly and stable.

As used herein, “stable” means that compounds disclosed herein does notprecipitate from or separated from the carrier solvent or otheringredients in the composition in about 1 hour, from about 1 hour toabout 12 hours, about 12 hours, about 1 day, about 5 days, about 10days, about 20 days, about 1 month, from about 1 month to about 1 year,or from about 1 year to about 2 year after the compounds disclosedherein and carrier solvent or any other ingredients are mixedhomogenously.

In some embodiments, the carrier solvent can be any inorganic or organicsolvent commonly used in industry or in laboratory. In some otherembodiments of the article, product, or composition, the carrier solventis water, an alcohol, an alkylene glycol, an alkyleneglycol alkyl ether,or a combination thereof. In some other embodiments, the carrier solventis methanol, ethanol, propanol, isopropanol, butanol, isobutanol,monoethyleneglycol, ethyleneglycol monobutyl ether, or a combinationthereof.

In some embodiments, the articles, products, or compositions are solid.In some other embodiments, the articles, products, or compositions areliquid.

In some embodiments, the article, product or composition can furthercomprise an additional surfactant. The additional surfactant is anonionic, semi-nonionic, anionic, cationic, amphoteric, zwitterionic,Gemini surfactant, or combinations thereof.

In some embodiments, the additional surfactant is a nonionic,semi-nonionic, anionic, cationic, amphoteric, zwitterionic, Geminisurfactant, or combinations thereof. In some embodiments, thecomposition disclosed here includes a normal surfactant but is free of aGemini surfactant. In some other embodiments, the composition includes aGemini surfactant, but is free of a normal surfactant. In yet some otherembodiments, the surfactant composition includes one kind of nonionic,semi-nonionic, anionic, cationic, amphoteric, and zwitterionicsurfactants, but is free of the rest of the surfactants. For example, adisclosed composition can include one or more compounds disclosed hereinand one or more nonionic surfactants, but is free of a semi-nonionic,anionic, cationic, amphoteric, zwitterionic, or Gemini surfactant.

In some embodiments, the article, product or composition disclosed herecomprises one or more compounds disclosed herein, an acid, and carriersolvent. In some embodiments, the article, product or compositiondisclosed here comprises one or more compounds disclosed herein, anacid, carrier solvent, and a peroxycarboxylic acid or peroxycarboxylicacid composition.

In some embodiments, the article, product or composition can furthercomprise a primary alkalinity source. In some embodiments, the article,product or composition disclosed here is a detergent composition thatcomprises one or more compounds disclosed herein and primary alkalinitysources. A detergent composition, as used herein, refers to acomposition that contains more primary alkalinity source than thecompounds disclosed herein in weight percentage and can generate analkaline use solution having a use solution pH of from about 8 to about13.

In some embodiments, the article, product or composition disclosed hereis a detergent composition that comprises one or more compoundsdisclosed herein, primary alkalinity sources, and chelants. In someembodiments, the article, product or composition disclosed here is adetergent composition that comprises one or more compounds disclosedherein, primary alkalinity sources, chelants, and surfactants. In someembodiments, the article, product or composition disclosed here is adetergent composition that comprises one or more compounds disclosedherein, primary alkalinity sources, and chelants, but is free of asurfactant.

In some embodiments, the compositions are solid compositions. In someother embodiments, the compositions are liquid.

In some embodiments, the article, product or composition disclosed hereis a detergent composition that comprises one or more compoundsdisclosed herein, primary alkalinity sources, and enzymes. In someembodiments, the article, product or composition disclosed here is adetergent composition that comprises one or more compounds disclosedherein, primary alkalinity sources, chelants, enzymes, and surfactants.In some embodiments, the article, product or composition disclosed hereis a detergent composition that comprises one or more compoundsdisclosed herein, primary alkalinity sources, and enzymes, but is freeof a surfactant, chelant, or both.

In some embodiments, the primary alkalinity source comprises an alkalimetal hydroxide, alkali metal carbonate, alkali metal silicate, alkalimetal silicate, amine, or mixture thereof In some other embodiments, theprimary alkalinity source comprises an alkali metal hydroxide, alkalimetal carbonate, or mixture thereof.

In some embodiments, the detergent composition disclosed herein includea builder. In some embodiments, the detergent composition disclosedherein is free of a builder but includes a part of the primaryalkalinity source as builder.

In some embodiments, the detergent composition disclosed herein includean enzyme, wherein the enzyme is amylase, protease, lipase, cellulase,cutinase, gluconase, peroxidase, and/or mixtures thereof. In someembodiments, the enzyme is a protease enzyme. In some other embodiments,the enzyme is a protease and amylase. In some other embodiments, theenzyme is a protease, amylase, and a lipase. In yet some otherembodiments, the detergent composition or composition disclosed hereinis free of an enzyme.

In some embodiments, the detergent composition or composition disclosedhere include a chelant, wherein the chelant is methylglycinediaceticacid (MGDA), glutamic acid-N,N-diacetic acid (GLDA),N-hydroxyethylaminodiacetic acid, ethylenediaminetetraacetic acid (EDTA)(including tetra sodium EDTA), hydroxyethylenediaminetetraacetic acid,diethylenetriaminepentaacetic acid,N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA),diethylenetriaminepentaacetic acid (DTPA), ethylenediaminesuccinic acid(EDDS), 2-hydroxyethyliminodiacetic acid (HEIDA), iminodisuccinic acid(IDS), 3-hydroxy-2-2′-iminodisuccinic acid (HIDS), or a mixture thereof.

In other embodiments, the detergent composition disclosed herein furtherinclude one or more addition detergent composition agents.

In some embodiments, the detergent compositions disclosed herein aresolid compositions. In some other embodiments, the detergentcompositions are liquid. In some embodiments, the solid detergentcompositions disclosed herein are any pressed, extruded, or cast solidcompositions, or in loose powder forms. In some other embodiments, thesolid detergent composition is pressed and/or extruded blocks. In someother embodiments, the detergent compositions are multiple-use pressedsolid block compositions.

A multi-use solid block detergent composition is preferred because thesolid block detergent composition provides solid state stability and canbe used in a dispenser. The use of solidification technology and solidblock detergents for institutional and industrial operations is setforth for example with respect to the SOLID POWER® brand technology suchas disclosed in U.S. Reissue Pat. Nos. 32,762 and 32,818. In someembodiments, the detergent compositions disclosed herein include sodiumcarbonate hydrate cast solid products as disclosed by Heile et al., U.S.Pat. Nos. 4,595,520 and 4,680,134. Each of these references are hereinincorporated by reference in its entirety. Without being limitedaccording to a mechanism of action, the solidification mechanism is ashhydration or the interaction of the sodium carbonate with water.

The methods and compositions of the present disclosure may comprise,consist essentially of, or consist of the components and ingredients ofthe disclosed compositions or methods as well as other ingredientsdescribed herein. As used herein, “consisting essentially of” means thatthe methods and compositions may include additional steps, components oringredients, but only if the additional steps, components or ingredientsdo not materially alter the basic and novel characteristics of theclaimed methods and compositions.

Alkalinity Source

The disclosed methods of preparation may include using an effectiveamount of an alkalinity source as a catalyst. The alkalinity source inturn comprises one or more alkaline compounds. The alkalinity source canbe added to the reaction mixture in the form of solid, liquid, orsolution thereof.

In general, an effective amount of the alkalinity source should beconsidered as an amount that provides a reaction mixture having a pH ofat least about 8. When the solution has a pH of between about 8 andabout 10, it can be considered mildly alkaline, and when the pH isgreater than about 12, the solution can be considered caustic.

The alkalinity source can include an alkali metal carbonate, an alkalimetal hydroxide, alkaline metal silicate, alkaline metal metasilicate,or a mixture thereof. Suitable metal carbonates that can be usedinclude, for example, sodium or potassium carbonate, bicarbonate,sesquicarbonate, or a mixture thereof. Suitable alkali metal hydroxidesthat can be used include, for example, sodium, lithium, or potassiumhydroxide. Examples of useful alkaline metal silicates include sodium orpotassium silicate (with M₂O:SiO₂ ratio of 2.4 to 5:1, M representing analkali metal) or metasilicate. A metasilicate can be made by mixing ahydroxide and silicate. The alkalinity source may also include a metalborate such as sodium or potassium borate, and the like.

The alkalinity source may also include ethanolamines, urea sulfate,amines, amine salts, and quaternary ammonium. The simplest cationicamines, amine salts and quaternary ammonium compounds can beschematically drawn thus:

in which, R represents a long alkyl chain, R′, R″, and R″′ may be eitherlong alkyl chains or smaller alkyl or aryl groups or hydrogen and Xrepresents an anion.

In some embodiments, the methods of preparation are free of thealkalinity source because the reactants contain a primary amine orprimary amine group to catalyze the reaction.

Primary Alkalinity Source

The disclosed composition can include a primary alkalinity source,especially when the disclosed composition is a detergent composition.

The primary alkalinity source of the composition or detergentcomposition disclosed herein can include, for example, an alkali metalhydroxide, alkali metal carbonate, alkali metal silicate, alkali metalmetasilicate or mixture thereof. Examples of suitable alkalinity sourcesinclude, but are not limited to, sodium hydroxide, potassium hydroxide,sodium carbonate, potassium carbonate, sodium silicate, sodiummetasilicate, potassium silicate, or a mixture thereof. The alkalinitysource is preferably an alkali hydroxide, alkali carbonate, or mixturethereof. The alkalinity source controls the pH of the resulting usesolution of the composition disclosed when water or other diluent isadded to the composition to form a use solution.

When the disclosed composition is a detergent composition, the pH of theuse solution must be maintained in the alkaline range to providesufficient detergency properties. Therefore, the disclosed detergentcomposition comprises more primary alkalinity source than the disclosedcompounds disclosed herein in term of weight percentage.

A use solution of a composition disclosed herein as used herein refersto a diluted solution for the composition or compounds by a diluent. Adiluent as used herein refers to water, city water, distilled water, orcarrier solvents defined herein. The composition or the compounds can bediluted by a factor of 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11-1,000,000,or any value there between to generate a use solution and then use theuse solution for this application. In this disclosure, when acomposition or di-cationic compounds are applied, either thecomposition/compounds or use solution thereof is applied.

When the disclosed composition is a detergent composition, the pH of ause solution of the detergent composition is defined as the pH that isdetermined at room temperature when the use solution is obtained bydiluting the detergent composition with distilled water and containsfrom 0.1 g/L to about 3 g/L of the primary alkalinity source. In someembodiments, the concentration of the alkalinity source is from about0.1 g/L to about 0.5 g/L, from about 0.5 g/L to about 1 g/L, from about1 g/L to about 3 g/L, from about 1 g/L to about 2 g/L, from about 2 g/Lto about 3 g/L, about 0.1 g/L, about 0.2 g/L, about 0.3 g/L, about 0.4g/L, about 0.5 g/L, about 1.0 g/L, about 1.5 g/L, about 2.0 g/L, about2.5 g/L, about 3.0 g/L, or any value there between in the use solution.

Alternatively, when the disclosed composition is a detergentcomposition, the pH of a use solution of the detergent composition isdefined as the pH that is determined at room temperature when the usesolution is obtained by diluting the detergent composition withdistilled water and contains from 0.5 g/L to about 5 g/L of thecomposition. In some embodiments, the concentration of the compositionis from about from about 0.5 g/L to about 1 g/L, from about 1 g/L toabout 2 g/L, from about 2 g/L to about 3 g/L, from about 3 g/L to about4 g/L, from about 4 g/L to about 5 g/L, about 0.5 g/L, about 1.0 g/L,about 1.5 g/L, about 2.0 g/L, about 2.5 g/L, about 3.0 g/L, about 3.5g/L, about 4.0 g/L, about 4.5 g/L, about 5.0 g/L or any value therebetween in the use solution.

In some embodiments, a use solution of the detergent compositiontherefore provides a pH of at least about 8, preferably a pH of fromabout 9.5 to about 12, more preferably from about 10 to about 11 or fromabout 11 to about 12, when its primary alkalinity source is at aconcentration of about 0.1 g/L, about 0.2 g/L, about 0.5 g/L, about 0.8g/L, or about 1 gram per liter (g/L). In some embodiments, a usesolution of the detergent composition therefore provides a pH of atleast 8, preferably a pH of 9.5 to 11, more preferably 10 to 11, fromabout 11 to about 12, when its primary alkalinity source in distilledwater is at a concentration of about 1 g/L, about 1.5 g/L, about 2.0g/L, about 2.5 g/L, about 3 g/L, or any value there between.

In some other embodiments, a use solution of the detergent compositiontherefore provides a pH of at least about 8, preferably a pH of fromabout 9.5 to about 12, more preferably from about 10 to about 11 or fromabout 11 to about 12, when the composition itself is at a concentrationof about 0.5 g/L, about 0.8 g/L, about 1 g/L, about 1.5 g/L, about 2.0g/L, about 2.5 g/L, about 3.0 g/L, about 3.5 g/L, about 4.0 g/L, about4.5 g/L, or about 5.0 g/L. In some embodiments, a use solution of thedetergent composition therefore provides a pH of at least 8, preferablya pH of 9.5 to 11, more preferably 10 to 11, from about 11 to about 12,when the composition itself is at a concentration of about 1 g/L, about1.5 g/L, about 2.0 g/L, about 2.5 g/L, about 3 g/L, about 3.5 g/L, about4.0, g/L, about 4.5 g/L, about 5.0 g/L, or any value there between.

In some embodiments, the pH of the use solution is between about 10 andabout 13. In some embodiments, the pH of the use solution is betweenabout 8 and about 10. Particularly, the pH of the use solution is about11-12. If the pH of the use solution is too low, for example, belowapproximately 10, the use solution may not provide adequate detergencyproperties. Further, at lower pH levels, the silicate species becomeunstable and may precipitate out of solution. If the pH of the usesolution is too high, for example, above approximately 13, the usesolution may be too alkaline and attack or damage the surface to becleaned. A further consideration for the pH is that if the compositionis too alkaline, a user would be required to wear PPE. However, if thepH of the composition is at or below about 11.5 pH, PPE is not required.Therefore, it is desirable for the pH of the detergent compositiondisclosed herein in diluted use form to be between about 11 and about 12for the composition to be effective, but not corrosive to human skin.

Preferably, the primary alkalinity source is an alkali metal hydroxide.Preferred alkali metal hydroxides include sodium hydroxide and potassiumhydroxide. More preferably, the primary alkalinity source is sodiumhydroxide. Sodium carbonate can be of light density or heavy density.

When a carbonate is included in the disclosed detergent composition, aneffective amount of the alkali metal carbonate is an amount thatprovides a use solution having a pH of at least 8, preferably a pH of9.5 to 11, more preferably 10 to 10.3.

In general, when the primary alkalinity source is present in thedisclosed detergent composition at a concentration of at least about 1wt-%, the composition or a use solution of the composition can emulsifyfats and oils present. When the primary alkalinity source is present ina concentration of about 3 wt-% or greater, the composition or a usesolution of the composition can emulsify, suspend, and separate oils andfats after treatment.

In some embodiments where the disclosed composition is not a detergentcomposition, the composition is free of a primary alkalinity source.

Acids

Generally, acids, as used in this disclosure, include both organic andinorganic acids. Organic acids include, but not limited to,hydroxyacetic (glycolic) acid, formic acid, acetic acid, propionic acid,butyric acid, valeric acid, caproic acid, gluconic acid, itaconic acid,trichloroacetic acid, urea hydrochloride, and benzoic acid. Organicacids also include dicarboxylic acids such as oxalic acid, malonic acid,succinic acid, glutaric acid, maleic acid, fumaric acid, adipic acid,and terephthalic acid. Combinations of these organic acids can also beused. Inorganic acids include, but are not limited to, mineral acids,such as phosphoric acid, sulfuric acid, sulfamic acid, methylsulfamicacid, hydrochloric acid, hydrobromic acid, hydrofluoric acid, and nitricacid. Inorganic acids can be used alone, in combination with otherinorganic acid(s), or in combination with one or more organic acid. Acidgenerators can be used to form a suitable acid, including for examplegenerators such as potassium fluoride, sodium fluoride, lithiumfluoride, ammonium fluoride, ammonium bifluoride, sodium silicofluoride,etc.

Examples of particularly suitable acids in this the methods orcompositions disclosed herein include inorganic and organic acids.Exemplary inorganic acids include phosphoric, phosphonic, sulfuric,sulfamic, methylsulfamic, hydrochloric, hydrobromic, hydrofluoric, andnitric. Exemplary organic acids include hydroxyacetic (glycolic),citric, lactic, formic, acetic, propionic, butyric, valeric, caproic,gluconic, itaconic, trichloroacetic, urea hydrochloride, and benzoic.Organic dicarboxylic acids can also be used such as oxalic, maleic,fumaric, adipic, and terephthalic acid.

Percarboxylic Acids and Peroxycarboxylic Acid Compositions

A peroxycarboxylic acid (i.e. peracid) or peroxycarboxylic acidcomposition can be included in the articles, products, or compositionsdisclosed herein. As used herein, the term “peracid” may also bereferred to as a “percarboxylic acid,” “peroxycarboxylic acid” or“peroxyacid.” Sulfoperoxycarboxylic acids, sulfonated peracids andsulfonated peroxycarboxylic acids are also included within the terms“peroxycarboxylic acid” and “peracid” as used herein. As one of skill inthe art appreciates, a peracid refers to an acid having the hydrogen ofthe hydroxyl group in carboxylic acid replaced by a hydroxy group.Oxidizing peracids may also be referred to herein as peroxycarboxylicacids.

A peracid includes any compound of the formula R—(COOOOH)_(n) in which Rcan be hydrogen, alkyl, alkenyl, alkyne, acylic, alicyclic group, aryl,heteroaryl, or heterocyclic group, and n is 1, 2, or 3, and named byprefixing the parent acid with peroxy. Preferably R includes hydrogen,alkyl, or alkenyl. The terms “alkyl,” “alkenyl,” “alkyne,” “acylic,”“alicyclic group,” “aryl,” “heteroaryl,” and “heterocyclic group” are asdefined herein.

A peroxycarboxylic acid composition, as used herein, refers to anycomposition that comprises one or more peracids, their correspondingacids, and hydrogen peroxide or or other oxidizing agents. Aperoxycarboxylic acid composition can also include a stabilizer,fluorescent active tracer or compound, or other ingredients, as oneskilled in the other would know.

As used herein, the terms “mixed” or “mixture” when used relating to“percarboxylic acid composition,” “percarboxylic acids,”“peroxycarboxylic acid composition” or “peroxycarboxylic acids” refer toa composition or mixture including more than one percarboxylic acid orperoxycarboxylic acid. Peracids such as peroxyacetic acid andperoxyoctanoic acid may also be used. Any combination of these acids mayalso be used.

In some embodiments, however, the articles, products, or compositionsdisclosed herein are free of a peroxycarboxylic acid or peroxycarboxylicacid composition.

Builder

The detergent compositions disclosed herein include one or morebuilders. In some embodiments, a builder may also serve as a part of theprimary alkalinity source in the detergent compositions. In someembodiments, the builder includes a carbonate, hydroxide, metasilicate,or mixture thereof In some embodiments, a carbonate can assist inproviding solid detergent compositions, as the carbonate can act as ahydratable salt.

Examples of suitable builders include, but are not limited to alkalimetal carbonates, alkali metal hydroxides, and alkali metal silicates.Exemplary alkali metal carbonates that can be used include, but are notlimited to, sodium or potassium carbonate, bicarbonate, sesquicarbonate,and mixtures thereof. Exemplary alkali metal hydroxides that can be usedinclude, but are not limited to, sodium or potassium hydroxide. Thealkali metal hydroxide may be added to the composition in any form knownin the art, including as solid beads, dissolved in an aqueous solution,or a combination thereof. Examples of alkali metal silicates include,but are not limited to, sodium or potassium silicate or polysilicate,sodium or potassium metasilicate and hydrated sodium or potassiummetasilicate or a combination thereof.

In some embodiments, the composition is free of a builder.

Chelant

The detergent composition disclosed herein may also include a chelant.Chelants include, but are not limited to, chelating agents (chelators),sequestering agents (sequestrants), detergent builders, and the like.Examples of chelants include, but are not limited to, phosphonates,phosphates, aminocarboxylates and their derivatives, pyrophosphates,polyphosphates, ethylenediamine and ethylenetriamine derivatives,hydroxyacids, and mono-, di-, and tri-carboxylates and theircorresponding acids. Other exemplary chelants include aluminosilicates,nitroloacetates and their derivatives, and mixtures thereof.

Suitable aminocarboxylic acids according to the invention include, butare not limited to, methylglycinediacetic acid (MGDA), glutamicacid-N,N-diacetic acid (GLDA), N-hydroxyethylaminodiacetic acid,ethylenediaminetetraacetic acid (EDTA) (including tetra sodium EDTA),hydroxyethylenediaminetetraacetic acid, diethylenetriaminepentaaceticacid, N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA),diethylenetriaminepentaacetic acid (DTPA), ethylenediaminesuccinic acid(EDDS), 2-hydroxyethyliminodiacetic acid (HEIDA), iminodisuccinic acid(IDS), 3-hydroxy-2-2′-iminodisuccinic acid (HIDS) and other similaracids or salts thereof having an amino group with a carboxylic acidsubstituent. Additional description of suitable aminocarboxylatessuitable for use as chelating agents and/or sequestrants is set forth inKirk-Othmer, Encyclopedia of Chemical Technology, Third Edition. volume5, pages 339-366 and volume 23, pages 319-320, the disclosure of whichis incorporated by reference herein.

Chelants can be water soluble, and/or biodegradable. Other exemplarychelants include TKPP (tetrapotassium pyrophosphate), PAA (polyacrylicacid) and its salts, phosphonobutane carboxylic acid, Alanine,N,N-bis(carboxymethyl)-, trisodium salt, and sodium gluconate.

In some embodiments, the chelant is free of phosphorus. In someembodiments, the chelant may also serve as a solidifying agent to helpform the solid composition, such as sodium salts of citric acid.

Preferably, the chelant is a sodium salt of aminocarboxylates. Morepreferably, the chelant is methyl glycine diacetic acid (MGDA).Synergistic water conditioning is achieved when using methyl glycinediacetic acid (MGDA) in combination with poly acrylic acids and itssalts.

In some embodiments, the composition disclosed herein is free of achelant, detergent builder, or both. In some embodiments, thecomposition disclosed herein is free of a chelant, detergent builder, orboth that contain phosphorus.

Scale Inhibitor

The reverse emulsion breaker composition can further comprise a scaleinhibitor. Suitable scale inhibitors include, but are not limited to,phosphates, phosphate esters, phosphoric acids, phosphonates, phosphonicacids, polyacrylamides, salts of Sacrylamidomethyl propanesulfonate/acrylic acid copolymer (AMPS/AA), phosphinated maleiccopolymer (PHOS/MA), mono-, bis- and oligomeric phosphinosuccinic acid(PSO) derivatives, polycarboxylic acid, hydrophobically modifiedpolycarboxylic acid, and salts of a polymaleic acid/acrylicacid/acrylamidomethyl propane sulfonate terpolymer (PMA/AA/AMPS).

In some embodiments, the composition disclosed herein is free of a scaleinhibitor.

Enzyme

The compositions or detergent compositions disclosed herein can includean enzyme. An enzyme in the detergent compositions enhances removal ofsoils, prevents re-deposition, and/or reduces foam during applicationsof the detergent compositions or their use solutions. The function of anenzyme is to break down adherent soils, such as starch or proteinaceousmaterials, typically found in soiled surfaces and removed by a detergentcomposition into a wash water source.

Exemplary types of enzymes which can be incorporated into the detergentcompositions disclosed herein include, but are not limited to, amylase,protease, lipase, cellulase, cutinase, gluconase, peroxidase, and/ormixtures thereof. A composition disclosed herein may employ more thanone enzyme, from any suitable origin, such as vegetable, animal,bacterial, fungal or yeast origin. In some embodiments, the enzyme is aprotease. As used herein, the terms “protease” or “proteinase” referenzymes that catalyze the hydrolysis of peptide bonds.

As one skilled in the art shall ascertain, enzymes are designed to workwith specific types of soils. For example, according to an embodiment ofthe invention, ware wash applications may use a protease enzyme as it iseffective at the high temperatures of the ware wash machines and iseffective in reducing protein-based soils. Protease enzymes areparticularly advantageous for cleaning soils containing protein, such asblood, cutaneous scales, mucus, grass, food (e.g., egg, milk, spinach,meat residue, tomato sauce), or the like. Protease enzymes are capableof cleaving macromolecular protein links of amino acid residues andconvert substrates into small fragments that are readily dissolved ordispersed into the aqueous use solution. Proteases are often referred toas detersive enzymes due to the ability to break soils through thechemical reaction known as hydrolysis. Protease enzymes can be obtained,for example, from Bacillus subtilis, Bacillus licheniformis andStreptomyces griseus. Protease enzymes are also commercially availableas serine endoproteases.

Examples of commercially-available protease enzymes are available underthe following trade names: Esperase, Purafect, Purafect L, Purafect Ox,Everlase, Liquanase, Savinase, Prime L, Prosperase and Blap.

The enzyme to be included into the detergent composition may be anindependent entity and/or may be formulated in combination with thedetergent composition. In some embodiments, the enzyme may be formulatedinto a detergent composition in either liquid or solid formulations. Inaddition, enzyme compositions may be formulated into various delayed orcontrolled release formulations. For example, a solid molded detergentcomposition may be prepared without the addition of heat. As a skilledartisan will appreciate, enzymes tend to become denatured by theapplication of heat and therefore use of enzymes within detergentcompositions require methods of forming detergent compositions that doesnot rely upon heat as a step in the formation process, such assolidification.

The enzyme composition may further be obtained commercially in a solid(i.e., puck, powder, etc.) or liquid formulation. Commercially-availableenzymes are generally combined with stabilizers, buffers, cofactors andinert vehicles. The actual active enzyme content depends upon the methodof manufacture, which is well known to a skilled artisan and suchmethods of manufacture are not critical to the present invention.

Alternatively, the enzyme composition may be provided separate from thedetergent composition, such as added directly to a use solution of adetergent composition or a wash liquor, or wash water of an application,e.g. dishwasher.

Other Additional Detergent Composition Agent

The detergent composition disclosed herein may include one or moreadditional detergent composition agents. Exemplary additional detergentcomposition agents include, but are not limited to, a threshold agent;crystal modifier; hardening agent; bleaching agent; peroxycarboxylicacid, peroxycarboxylic acid composition, filler; defoaming agent;anti-redeposition agent; stabilizing agent; dispersant; fragrance anddye; and thickener.

In some embodiments, the detergent composition disclosed herein is freeof one, more, or all the additional detergent composition agents.

Anionic Surfactants

Anionic surfactants are surface active substances in which the charge onthe hydrophobe is negative; or surfactants in which the hydrophobicsection of the molecule carries no charge unless the pH is elevated toneutrality or above (e.g., carboxylic acids). Carboxylate, sulfonate,sulfate and phosphate are the polar (hydrophilic) solubilizing groupsfound in anionic surfactants. Of the cations (counter ions) associatedwith these polar groups, sodium, lithium and potassium impart watersolubility; ammonium and substituted ammonium ions provide both waterand oil solubility; and, calcium, barium, and magnesium promote oilsolubility. As those skilled in the art understand, anionic surfactantsare excellent detersive surfactants and are therefore favored additionsto heavy duty detergent compositions.

Anionic sulfate surfactants suitable for use in the present compositionsinclude alkyl ether sulfates, alkyl sulfates, the linear and branchedprimary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleylglycerol sulfates, alkyl phenol ethylene oxide ether sulfates, theC₅-C₁₇ acyl-N-(C₁-C₄ alkyl) and —N—(C₁-C₂ hydroxyalkyl) glucaminesulfates, and sulfates of alkylpolysaccharides such as the sulfates ofalkylpolyglucoside, and the like. Also included are the alkyl sulfates,alkyl poly(ethyleneoxy) ether sulfates and aromatic poly(ethyleneoxy)sulfates such as the sulfates or condensation products of ethylene oxideand nonyl phenol (usually having 1 to 6 oxyethylene groups permolecule).

Anionic sulfonate surfactants suitable for use in the presentcompositions also include alkyl sulfonates, the linear and branchedprimary and secondary alkyl sulfonates, and the aromatic sulfonates withor without substituents.

Anionic carboxylate surfactants suitable for use in the presentcompositions include carboxylic acids (and salts), such as alkanoicacids (and alkanoates), ester carboxylic acids (e.g., alkyl succinates),ether carboxylic acids, sulfonated fatty acids, such as sulfonated oleicacid, and the like. Such carboxylates include alkyl ethoxy carboxylates,alkyl aryl ethoxy carboxylates, alkyl polyethoxy polycarboxylatesurfactants and soaps (e.g., alkyl carboxyls). Secondary carboxylatesuseful in the present compositions include those which contain acarboxyl unit connected to a secondary carbon. The secondary carbon canbe in a ring structure, e.g., as in p-octyl benzoic acid, or as inalkyl-substituted cyclohexyl carboxylates. The secondary carboxylatesurfactants typically contain no ether linkages, no ester linkages andno hydroxyl groups. Further, they typically lack nitrogen atoms in thegroup-group (amphiphilic portion). Suitable secondary soap surfactantstypically contain 11-13 total carbon atoms, although more carbons atoms(e.g., up to 16) can be present. Suitable carboxylates also includeacylamino acids (and salts), such as acylgluamates, acyl peptides,sarcosinates (e.g., N-acyl sarcosinates), taurates (e.g., N-acyltaurates and fatty acid amides of methyl tauride), and the like.

Suitable anionic surfactants include alkyl or alkylaryl ethoxycarboxylates of the following formula:R—O—(CH₂CH₂O)_(n)(CH₂)_(m)—CO₂X   (3)in which R is a C₈ to C₂₂ alkyl group or

in which R¹ is a C₄-C₁₆ alkyl group; n is an integer of 1-20; m is aninteger of 1-3; and X is a counter ion, such as hydrogen, sodium,potassium, lithium, ammonium, or an amine salt such as monoethanolamine,diethanolamine or triethanolamine. In some embodiments, n is an integerof 4 to 10 and m is 1. In some embodiments, R is a C₈-C₁₆ alkyl group.In some embodiments, R is a C₁₂-C₁₄ alkyl group, n is 4, and m is 1.

In other embodiments, R is

and R¹ is a C₆-C₁₂ alkyl group. In still yet other embodiments, R¹ is aC₉ alkyl group, n is 10 and m is 1.

Such alkyl and alkylaryl ethoxy carboxylates are commercially available.These ethoxy carboxylates are typically available as the acid forms,which can be readily converted to the anionic or salt form. Commerciallyavailable carboxylates include, Neodox 23-4, a C₁₂₋₁₃ alkyl polyethoxy(4) carboxylic acid (Shell Chemical), and Emcol CNP-110, a C₉ alkylarylpolyethoxy (10) carboxylic acid (Witco Chemical). Carboxylates are alsoavailable from Clariant, e.g., the product Sandopan® DTC, a C₁₃ alkylpolyethoxy (7) carboxylic acid.

In some embodiments, the composition or detergent composition disclosedherein is free of an anionic surfactant.

Nonionic Surfactants

Useful nonionic surfactants are generally characterized by the presenceof an organic hydrophobic group and an organic hydrophilic group and aretypically produced by the condensation of an organic aliphatic, alkylaromatic or polyoxyalkylene hydrophobic compound with a hydrophilicalkaline oxide moiety which in common practice is ethylene oxide or apolyhydration product thereof, polyethylene glycol. Practically anyhydrophobic compound having a hydroxyl, carboxyl, amino, or amido groupwith a reactive hydrogen atom can be condensed with ethylene oxide, orits polyhydration adducts, or its mixtures with alkoxylenes such aspropylene oxide to form a nonionic surface-active agent. The length ofthe hydrophilic polyoxyalkylene moiety which is condensed with anyparticular hydrophobic compound can be readily adjusted to yield a waterdispersible or water-soluble compound having the desired degree ofbalance between hydrophilic and hydrophobic properties. Useful nonionicsurfactants include:

Block polyoxypropylene-polyoxyethylene polymeric compounds based uponpropylene glycol, ethylene glycol, glycerol, trimethylolpropane, andethylenediamine as the initiator reactive hydrogen compound. Examples ofpolymeric compounds made from a sequential propoxylation andethoxylation of initiator are commercially available from BASF Corp. Oneclass of compounds are difunctional (two reactive hydrogens) compoundsformed by condensing ethylene oxide with a hydrophobic base formed bythe addition of propylene oxide to the two hydroxyl groups of propyleneglycol. This hydrophobic portion of the molecule weighs from about 1,000to about 4,000. Ethylene oxide is then added to sandwich this hydrophobebetween hydrophilic groups, controlled by length to constitute fromabout 10% by weight to about 80% by weight of the final molecule.Another class of compounds are tetra-flinctional block copolymersderived from the sequential addition of propylene oxide and ethyleneoxide to ethylenediamine. The molecular weight of the propylene oxidehydrotype ranges from about 500 to about 7,000; and, the hydrophile,ethylene oxide, is added to constitute from about 10% by weight to about80% by weight of the molecule.

Condensation products of one mole of alkyl phenol wherein the alkylchain, of straight chain or branched chain configuration, or of singleor dual alkyl constituent, contains from about 8 to about 18 carbonatoms with from about 3 to about 50 moles of ethylene oxide. The alkylgroup can, for example, be represented by diisobutylene, di-amyl,polymerized propylene, iso-octyl, nonyl, and di-nonyl. These surfactantscan be polyethylene, polypropylene, and polybutylene oxide condensatesof alkyl phenols. Examples of commercial compounds of this chemistry areavailable on the market under the trade names Igepal® manufactured byRhone-Poulenc and Triton® manufactured by Union Carbide.

Condensation products of one mole of a saturated or unsaturated,straight or branched chain alcohol having from about 6 to about 24carbon atoms with from about 3 to about 50 moles of ethylene oxide. Thealcohol moiety can consist of mixtures of alcohols in the abovedelineated carbon range or it can consist of an alcohol having aspecific number of carbon atoms within this range. Examples of likecommercial surfactant are available under the trade names Lutensol™,Dehydol™ manufactured by BASF, Neodol™ manufactured by Shell ChemicalCo. and Alfonic™ manufactured by Vista Chemical Co.

Condensation products of one mole of saturated or unsaturated, straightor branched chain carboxylic acid having from about 8 to about 18 carbonatoms with from about 6 to about 50 moles of ethylene oxide. The acidmoiety can consist of mixtures of acids in the above defined carbonatoms range or it can consist of an acid having a specific number ofcarbon atoms within the range. Examples of commercial compounds of thischemistry are available on the market under the trade names Disponil orAgnique manufactured by BASF and Lipopeg™ manufactured by LipoChemicals, Inc.

In addition to ethoxylated carboxylic acids, commonly calledpolyethylene glycol esters, other alkanoic acid esters formed byreaction with glycerides, glycerin, and polyhydric (saccharide orsorbitan/sorbitol) alcohols have application in this invention forspecialized embodiments, particularly indirect food additiveapplications. All of these ester moieties have one or more reactivehydrogen sites on their molecule which can undergo further acylation orethylene oxide (alkoxide) addition to control the hydrophilicity ofthese substances. Care must be exercised when adding these fatty estersor acylated carbohydrates to compositions of the present inventioncontaining amylase and/or lipase enzymes because of potentialincompatibility.

Examples of nonionic low foaming surfactants include, but are notlimited to, compounds which are modified, essentially reversed, byadding ethylene oxide to ethylene glycol to provide a hydrophile ofdesignated molecular weight; and, then adding propylene oxide to obtainhydrophobic blocks on the outside (ends) of the molecule. Thehydrophobic portion of the molecule weighs from about 1,000 to about3,100 with the central hydrophile including 10% by weight to about 80%by weight of the final molecule. These reverse Pluronics™ aremanufactured by BASF Corporation under the trade name Pluronic™ Rsurfactants. Likewise, the Tetronic™ R surfactants are produced by BASFCorporation by the sequential addition of ethylene oxide and propyleneoxide to ethylenediamine. The hydrophobic portion of the molecule weighsfrom about 2,100 to about 6,700 with the central hydrophile including10% by weight to 80% by weight of the final molecule.

Compounds which are modified by “capping” or “end blocking” the terminalhydroxy group or groups (of multi-functional moieties) to reduce foamingby reaction with a small hydrophobic molecule such as propylene oxide,butylene oxide, benzyl chloride; and, short chain fatty acids, alcoholsor alkyl halides containing from 1 to about 5 carbon atoms; and mixturesthereof. Also included are reactants such as thionyl chloride whichconvert terminal hydroxy groups to a chloride group. Such modificationsto the terminal hydroxy group may lead to all-block, block-heteric,heteric-block or all-heteric nonionics.

Additional examples of effective low foaming nonionic surfactantsinclude, but are not limited to the alkylphenoxypolyethoxyalkanols ofU.S. Pat. No. 2,903,486 issued Sep. 8, 1959 to Brown et al. andrepresented by the formula

in which R is an alkyl group of 8 to 9 carbon atoms, A is an alkylenechain of 3 to 4 carbon atoms, n is an integer of 7 to 16, and m is aninteger of 1 to 10.

The polyalkylene glycol condensates of U.S. Pat. No. 3,048,548 issuedAug. 7, 1962 to Martin et al. having alternated hydrophilic oxyethylenechains and hydrophobic oxypropylene chains where the weight of theterminal hydrophobic chains, the weight of the middle hydrophobic unitand the weight of the linking hydrophilic units each represent aboutone-third of the condensate.

The defoaming nonionic surfactants disclosed in U.S. Pat. No. 3,382,178issued May 7, 1968 to Lissant et al. having the general formulaZ[(OR)_(n)OH]_(z) wherein Z is alkoxylatable material, R is a radicalderived from an alkylene oxide which can be ethylene and propylene and nis an integer from, for example, 10 to 2,000 or more and z is an integerdetermined by the number of reactive oxyalkylatable groups.

The conjugated polyoxyalkylene compounds described in U.S. Pat. No.2,677,700, issued May 4, 1954 to Jackson et al. corresponding to theformula Y(C₃H₆O)_(n) (C₂H₄O)_(m)H wherein Y is the residue of organiccompound having from about 1 to 6 carbon atoms and one reactive hydrogenatom, n has an average value of at least about 6.4, as determined byhydroxyl number and m has a value such that the oxyethylene portionconstitutes about 10% to about 90% by weight of the molecule.

The conjugated polyoxyalkylene compounds described in U.S. Pat. No.2,674,619, issued Apr. 6, 1954 to Lundsted et al. having the formulaY[(C₃H₆O_(n) (C₂H₄O)_(m)H]_(x) wherein Y is the residue of an organiccompound having from about 2 to 6 carbon atoms and containing x reactivehydrogen atoms in which x has a value of at least about 2, n has a valuesuch that the molecular weight of the polyoxypropylene hydrophobic baseis at least about 900 and m has value such that the oxyethylene contentof the molecule is from about 10% to about 90% by weight. Compoundsfalling within the scope of the definition for Y include, for example,propylene glycol, glycerine, pentaerythritol, trimethylolpropane,ethylenediamine and the like. The oxypropylene chains optionally, butadvantageously, contain small amounts of ethylene oxide and theoxyethylene chains also optionally, but advantageously, contain smallamounts of propylene oxide.

Additional conjugated polyoxyalkylene surface-active agents which areadvantageously used in the compositions of this invention correspond tothe formula: P[(C₃H₆O)_(n) (C₂H₄O)_(m)H]_(x) wherein P is the residue ofan organic compound having from about 8 to 18 carbon atoms andcontaining x reactive hydrogen atoms in which x has a value of 1 or 2, nhas a value such that the molecular weight of the polyoxyethyleneportion is at least about 44 and m has a value such that theoxypropylene content of the molecule is from about 10% to about 90% byweight. In either case the oxypropylene chains may contain optionally,but advantageously, small amounts of ethylene oxide and the oxyethylenechains may contain also optionally, but advantageously, small amounts ofpropylene oxide.

Polyhydroxy fatty acid amide surfactants suitable for use in the presentcompositions include those having the structural formula R₂CON_(R1)Z inwhich: R1 is H, C₁-C₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl,ethoxy, propoxy group, or a mixture thereof; R₂ is a C₅-C₃₁ hydrocarbyl,which can be straight-chain; and Z is a polyhydroxyhydrocarbyl having alinear hydrocarbyl chain with at least 3 hydroxyls directly connected tothe chain, or an alkoxylated derivative (preferably ethoxylated orpropoxylated) thereof. Z can be derived from a reducing sugar in areductive amination reaction; such as a glycityl moiety.

The alkyl ethoxylate condensation products of aliphatic alcohols withfrom about 0 to about 25 moles of ethylene oxide are suitable for use inthe present compositions. The alkyl chain of the aliphatic alcohol caneither be straight or branched, primary or secondary, and generallycontains from 6 to 22 carbon atoms.

The ethoxylated C₆-C₁₈ fatty alcohols and C₆-C₁₈ mixed ethoxylated andpropoxylated fatty alcohols are suitable surfactants for use in thepresent compositions, particularly those that are water soluble.Suitable ethoxylated fatty alcohols include the C₆-C₁₈ ethoxylated fattyalcohols with a degree of ethoxylation of from 3 to 50.

Suitable nonionic alkylpolysaccharide surfactants, particularly for usein the present compositions include those disclosed in U.S. Pat. No.4,565,647, Llenado, issued Jan. 21, 1986. These surfactants include ahydrophobic group containing from about 6 to about 30 carbon atoms and apolysaccharide, e.g., a polyglycoside, hydrophilic group containing fromabout 1.3 to about 10 saccharide units. Any reducing saccharidecontaining 5 or 6 carbon atoms can be used, e.g., glucose, galactose andgalactosyl moieties can be substituted for the glucosyl moieties.(Optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc.positions thus giving a glucose or galactose as opposed to a glucosideor galactoside). The inter-saccharide bonds can be, e.g., between theone position of the additional saccharide units and the 2-, 3-, 4-,and/or 6-positions on the preceding saccharide units.

Fatty acid amide surfactants suitable for use the present compositionsinclude those having the formula: R₆CON(R₇)₂ in which R₆ is an alkylgroup containing from 7 to 21 carbon atoms and each R₇ is independentlyhydrogen, C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, or —(C₂H₄O)_(x)H, where x isin the range of from 1 to 3.

A useful class of non-ionic surfactants include the class defined asalkoxylated amines or, most particularly, alcoholalkoxylated/aminated/alkoxylated surfactants. These non-ionicsurfactants may be at least in part represented by the general formulae:R²⁰—(PO)_(S)N—(EO)_(t)H, R²⁰—(PO)_(S)N—(EO)_(t)H(EO)_(t)H, andR²⁰—N(EO)_(t)H; in which R²⁰ is an alkyl, alkenyl or other aliphaticgroup, or an alkyl-aryl group of from 8 to 20, preferably 12 to 14carbon atoms, EO is oxyethylene, PO is oxypropylene, s is 1 to 20,preferably 2-5, t is 1-10, preferably 2-5, and u is 1-10, preferably2-5. Other variations on the scope of these compounds may be representedby the alternative formula: R²⁰—(PO)_(V)—N[(EO)_(w)H] [(EO)_(z)H] inwhich R²⁰ is as defined above, v is 1 to 20 (e.g., 1, 2, 3, or 4(preferably 2)), and w and z are independently 1-10, preferably 2-5.These compounds are represented commercially by a line of products soldby Huntsman Chemicals as nonionic surfactants. A preferred chemical ofthis class includes Surfonic™ PEA 25 Amine Alkoxylate. Preferrednonionic surfactants for the compositions of the invention includealcohol alkoxylates, EO/PO block copolymers, alkylphenol alkoxylates,and the like.

The treatise Nonionic Surfactants, edited by Schick, M. J., Vol. 1 ofthe Surfactant Science Series, Marcel Dekker, Inc., New York, 1983 is anexcellent reference on the wide variety of nonionic compounds generallyemployed in the practice of the present invention. A typical listing ofnonionic classes, and species of these surfactants, is given in U.S.Pat. No. 3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975.Further examples are given in “Surface Active Agents and detergents”(Vol. I and II by Schwartz, Perry and Berch).

Suitable nonionic surfactants suitable for use with the compositions ofthe present invention include alkoxylated surfactants. Suitablealkoxylated surfactants include EO/PO copolymers, fully capped orpartially EO/PO copolymers, alcohol alkoxylates, capped alcoholalkoxylates, mixtures thereof, or the like. Suitable alkoxylatedsurfactants for use as solvents include EO/PO block copolymers, such asthe Pluronic and reverse Pluronic surfactants; alcohol alkoxylates, suchas Dehypon LS-54 (R-(EO)₅(PO)₄) and Dehypon LS-36 (R-(EO)₃(PO)₆); andcapped alcohol alkoxylates, such as Plurafac LF221 and Tegoten EC11;mixtures thereof, or the like.

In some embodiments that are not detergent compositions, the compositiondisclosed herein is free of a nonionic surfactant.

Semi-Polar Nonionic Surfactants

The semi-polar type of nonionic surfactants are another class ofnonionic surfactants useful in compositions disclosed herein. Generally,semi-polar nonionic surfactants are high foaming agents and foamstabilizers, which can limit their application in CIP systems. However,in some embodiments designed for high foaming composition or detergentcomposition, semi-polar nonionic surfactants would have immediateutility. The semi-polar nonionic surfactants include, but are notlimited to, the amine oxides, phosphine oxides, sulfoxides and theiralkoxylated derivatives.

Amine oxides are tertiary amine oxides corresponding to the generalformula:

wherein the arrow is a conventional representation of a semi-polar bond;and, R¹, R², and R³ may be aliphatic, aromatic, heterocyclic, alicyclic,or combinations thereof. Generally, for amine oxides of detergentinterest, R¹ is an alkyl radical of from about 8 to about 24 carbonatoms; R² and R³ are alkyl or hydroxyalkyl of 1-3 carbon atoms or amixture thereof; R² and R³ can be attached to each other, e.g. throughan oxygen or nitrogen atom, to form a ring structure; R⁴ is an alkyleneor a hydroxyalkylene group containing 2 to 3 carbon atoms; and n rangesfrom 0 to about 20.

Useful water soluble amine oxide surfactants are selected from thecoconut or tallow alkyl di-(lower alkyl) amine oxides, specific examplesof which are dodecyldimethylamine oxide, tridecyldimethylamine oxide,etradecyldimethylamine oxide, pentadecyldimethylamine oxide,hexadecyldimethylamine oxide, heptadecyldimethylamine oxide,octadecyldimethylaine oxide, dodecyldipropylamine oxide,tetradecyldipropylamine oxide, hexadecyldipropylamine oxide,tetradecyldibutylamine oxide, octadecyldibutylamine oxide,bis(2-hydroxyethyl)dodecylamine oxide,bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide,dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamineoxide and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

Useful semi-polar nonionic surfactants also include the water-solublephosphine oxides having the following structure:

wherein the arrow is a conventional representation of a semi-polar bond;and, R¹ is an alkyl, alkenyl or hydroxyalkyl moiety ranging from 10 toabout 24 carbon atoms in chain length; and, R² and R³ are each alkylmoieties separately selected from alkyl or hydroxyalkyl groupscontaining 1 to 3 carbon atoms.

Examples of useful phosphine oxides include dimethyldecylphosphineoxide, dimethyltetradecylphosphine oxide, methylethyltetradecylphosphoneoxide, dimethylhexadecylphosphine oxide,diethyl-2-hydroxyoctyldecylphosphine oxide,bis(2-hydroxyethyl)dodecylphosphine oxide, andbis(hydroxymethyl)tetradecylphosphine oxide.

Semi-polar nonionic surfactants useful herein also include the watersoluble sulfoxide compounds which have the structure:

wherein the arrow is a conventional representation of a semi-polar bond;and, R¹ is an alkyl or hydroxyalkyl moiety of about 8 to about 28 carbonatoms, from 0 to about 5 ether linkages and from 0 to about 2 hydroxylsubstituents; and R² is an alkyl moiety consisting of alkyl andhydroxyalkyl groups having 1 to 3 carbon atoms.

Useful examples of these sulfoxides include dodecyl methyl sulfoxide;3-hydroxy tridecyl methyl sulfoxide; 3-methoxy tridecyl methylsulfoxide; and 3-hydroxy-4-dodecoxybutyl methyl sulfoxide.

Semi-polar nonionic surfactants for the compositions of the inventioninclude dimethyl amine oxides, such as lauryl dimethyl amine oxide,myristyl dimethyl amine oxide, cetyl dimethyl amine oxide, combinationsthereof, and the like. Useful water soluble amine oxide surfactants areselected from the octyl, decyl, dodecyl, isododecyl, coconut, or tallowalkyl di-(lower alkyl) amine oxides, specific examples of which areoctyldimethylamine oxide, nonyldimethylamine oxide, decyldimethylamineoxide, undecyldimethylamine oxide, dodecyldimethylamine oxide,iso-dodecyldimethyl amine oxide, tridecyldimethylamine oxide,tetradecyldimethylamine oxide, pentadecyldimethylamine oxide,hexadecyldimethylamine oxide, heptadecyldimethylamine oxide,octadecyldimethylaine oxide, dodecyldipropylamine oxide,tetradecyldipropylamine oxide, hexadecyldipropylamine oxide,tetradecyldibutylamine oxide, octadecyldibutylamine oxide,bis(2-hydroxyethyl)dodecylamine oxide,bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide,dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamineoxide and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

In some embodiments, the composition or detergent composition disclosedherein is free of a semi-polar nonionic surfactant.

Cationic Surfactants

Surface active substances are classified as cationic if the charge onthe hydrotrope portion of the molecule is positive. Surfactants in whichthe hydrotrope carries no charge unless the pH is lowered close toneutrality or lower, but which are then cationic (e.g. alkyl amines),are also included in this group. In theory, cationic surfactants may besynthesized from any combination of elements containing an “onium”structure RnX+Y— and could include compounds other than nitrogen(ammonium) such as phosphorus (phosphonium) and sulfur (sulfonium). Inpractice, the cationic surfactant field is dominated by nitrogencontaining compounds, probably because synthetic routes to nitrogenouscationics are simple and straightforward and give high yields ofproduct, which can make them less expensive.

Cationic surfactants preferably include, more preferably refer to,compounds containing at least one long carbon chain hydrophobic groupand at least one positively charged nitrogen. The long carbon chaingroup may be attached directly to the nitrogen atom by simplesubstitution; or more preferably indirectly by a bridging functionalgroup or groups in so-called interrupted alkylamines and amido amines.Such functional groups can make the molecule more hydrophilic and/ormore water dispersible, more easily water solubilized by co-surfactantmixtures, and/or water soluble. For increased water solubility,additional primary, secondary or tertiary amino groups can beintroduced, or the amino nitrogen can be quaternized with low molecularweight alkyl groups. Further, the nitrogen can be a part of branched orstraight chain moiety of varying degrees of unsaturation or of asaturated or unsaturated heterocyclic ring. In addition, cationicsurfactants may contain complex linkages having more than one cationicnitrogen atom.

The surfactant compounds classified as amine oxides, amphoterics andzwitterions are themselves typically cationic in near neutral to acidicpH solutions and can overlap surfactant classifications.Polyoxyethylated cationic surfactants generally behave like nonionicsurfactants in alkaline solution and like cationic surfactants in acidicsolution.

The simplest cationic amines, amine salts and quaternary ammoniumcompounds can be schematically drawn thus:

in which, R represents an alkyl chain, R′, R″, and R′″ may be eitheralkyl chains or aryl groups or hydrogen and X represents an anion. Theamine salts and quaternary ammonium compounds are preferred forpractical use in this invention due to their high degree of watersolubility.

Most large volume commercial cationic surfactants can be subdivided intofour major classes and additional sub-groups known to those skilled inthe art and described in “Surfactant Encyclopedia”, Cosmetics &Toiletries, Vol. 104 (2) 86-96 (1989). The first class includesalkylamines and their salts. The second class includes alkylimidazolines. The third class includes ethoxylated amines. The fourthclass includes quaternaries, such as alkylbenzyldimethylammonium salts,alkyl benzene salts, heterocyclic ammonium salts, tetra alkylammoniumsalts, and the like. Cationic surfactants are known to have a variety ofproperties that can be beneficial in the present compositions. Thesedesirable properties can include detergency in compositions of or belowneutral pH, antimicrobial efficacy, thickening or gelling in cooperationwith other agents, and the like.

Cationic surfactants useful in the compositions disclosed herein includethose having the formula R¹ _(m)R² _(x)Y_(L)Z wherein each R¹ is anorganic group containing a straight or branched alkyl or alkenyl groupoptionally substituted with up to three phenyl or hydroxy groups andoptionally interrupted by up to four of the following structures:

or an isomer or mixture of these structures, and which contains fromabout 8 to 22 carbon atoms. The R¹ groups can additionally contain up to12 ethoxy groups. m is a number from 1 to 3. Preferably, no more thanone R¹ group in a molecule has 16 or more carbon atoms when m is 2 ormore than 12 carbon atoms when m is 3. Each R² is an alkyl orhydroxyalkyl group containing from 1 to 4 carbon atoms or a benzyl groupwith no more than one R² in a molecule being benzyl, and x is a numberfrom 0 to 11, preferably from 0 to 6. The remainder of any carbon atompositions on the Y group are filled by hydrogens.

Y is can be a group including, but not limited to:

or a mixture thereof. Preferably, L is 1 or 2, with the Y groups beingseparated by a moiety selected from R¹ and R² analogs (preferablyalkylene or alkenylene) having from 1 to about 22 carbon atoms and twofree carbon single bonds when L is 2. Z is a water-soluble anion, suchas a halide, sulfate, methylsulfate, hydroxide, or nitrate anion,particularly preferred being chloride, bromide, iodide, sulfate ormethyl sulfate anions, in a number to give electrical neutrality of thecationic component.

In some embodiments, the composition or detergent composition disclosedherein is free of a cationic surfactant.

Amphoteric Surfactants

Amphoteric, or ampholytic, surfactants contain both a basic and anacidic hydrophilic group and an organic hydrophobic group. These ionicentities may be any of anionic or cationic groups described herein forother types of surfactants. A basic nitrogen and an acidic carboxylategroup are the typical functional groups employed as the basic and acidichydrophilic groups. In a few surfactants, sulfonate, sulfate,phosphonate or phosphate provide the negative charge.

Amphoteric surfactants can be broadly described as derivatives ofaliphatic secondary and tertiary amines, in which the aliphatic radicalmay be straight chain or branched and wherein one of the aliphaticsubstituents contains from about 8 to 18 carbon atoms and one containsan anionic water solubilizing group, e.g., carboxy, sulfo, sulfato,phosphato, or phosphono. Amphoteric surfactants are subdivided into twomajor classes known to those of skill in the art and described in“Surfactant Encyclopedia” Cosmetics & Toiletries, Vol. 104 (2) 69-71(1989), which is herein incorporated by reference in its entirety. Thefirst class includes acyl/dialkyl ethylenediamine derivatives (e.g.2-alkyl hydroxyethyl imidazoline derivatives) and their salts. Thesecond class includes N-alkylamino acids and their salts. Someamphoteric surfactants can be envisioned as fitting into both classes.

Amphoteric surfactants can be synthesized by methods known to those ofskill in the art. For example, 2-alkyl hydroxyethyl imidazoline issynthesized by condensation and ring closure of a long chain carboxylicacid (or a derivative) with dialkyl ethylenediamine. Commercialamphoteric surfactants are derivatized by subsequent hydrolysis andring-opening of the imidazoline ring by alkylation—for example withchloroacetic acid or ethyl acetate. During alkylation, one or twocarboxy-alkyl groups react to form a tertiary amine and an ether linkagewith differing alkylating agents yielding different tertiary amines.

Long chain imidazole derivatives having application in the presentinvention generally have the general formula:

wherein R is an acyclic hydrophobic group containing from about 8 to 18carbon atoms and M is a cation to neutralize the charge of the anion,generally sodium. Commercially prominent imidazoline-derived amphotericsthat can be employed in the present compositions include for example:Cocoamphopropionate, Cocoamphocarboxy-propionate, Cocoamphoglycinate,Cocoamphocarboxy-glycinate, Cocoamphopropyl-sulfonate, andCocoamphocarboxy-propionic acid. Amphocarboxylic acids can be producedfrom fatty imidazolines in which the dicarboxylic acid functionality ofthe amphodicarboxylic acid is diacetic acid and/or dipropionic acid.

The carboxymethylated compounds (glycinates) described herein abovefrequently are called betaines. Betaines are a special class ofamphoteric discussed herein below in the section entitled, ZwitterionSurfactants.

Long chain N-alkylamino acids are readily prepared by reaction RNH₂, inwhich R═C₈-C₁₈ straight or branched chain alkyl, fatty amines withhalogenated carboxylic acids. Alkylation of the primary amino groups ofan amino acid leads to secondary and tertiary amines. Alkyl substituentsmay have additional amino groups that provide more than one reactivenitrogen center. Most commercial N-alkylamine acids are alkylderivatives of beta-alanine or beta-N(2-carboxyethyl) alanine. Examplesof commercial N-alkylamino acid ampholytes having application in thisinvention include alkyl beta-amino dipropionates, RN(C₂H₄COOM)₂ andRNHC₂H₄COOM. In an embodiment, R can be an acyclic hydrophobic groupcontaining from about 8 to about 18 carbon atoms, and M is a cation toneutralize the charge of the anion.

Suitable amphoteric surfactants include those derived from coconutproducts such as coconut oil or coconut fatty acid. Additional suitablecoconut derived surfactants include as part of their structure anethylenediamine moiety, an alkanolamide moiety, an amino acid moiety,e.g., glycine, or a combination thereof; and an aliphatic substituent offrom about 8 to 18 (e.g., 12) carbon atoms. Such a surfactant can alsobe considered an alkyl amphodicarboxylic acid. These amphotericsurfactants can include chemical structures represented as:C₁₂-alkyl-C(O)—NH—CH₂—CH₂—N⁺(CH₂—CH₂—CO₂Na)₂—CH₂—CH₂—OH orC₁₂-alkyl-C(O)—N(H)—CH₂—CH₂—N⁺(CH₂—CO₂Na)₂—CH₂—CH₂—OH. Disodiumcocoampho dipropionate is one suitable amphoteric surfactant and iscommercially available under the tradename Miranol™ FBS from RhodiaInc., Cranbury, N.J. Another suitable coconut derived amphotericsurfactant with the chemical name disodium cocoampho diacetate is soldunder the tradename Mirataine™ JCHA, also from Rhodia Inc., Cranbury,N.J.

A typical listing of amphoteric classes, and species of thesesurfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin andHeuring on Dec. 30, 1975. Further examples are given in “Surface ActiveAgents and Detergents” (Vol. I and II by Schwartz, Perry and Berch).Each of these references are herein incorporated by reference in theirentirety.

In some embodiments, the composition or detergent composition disclosedherein is free of an amphoteric surfactant.

Zwitterionic Surfactants

Zwitterionic surfactants can be thought of as a subset of the amphotericsurfactants and can include an anionic charge. Zwitterionic surfactantscan be broadly described as derivatives of secondary and tertiaryamines, derivatives of heterocyclic secondary and tertiary amines, orderivatives of quaternary ammonium, quaternary phosphonium or tertiarysulfonium compounds. Typically, a zwitterionic surfactant includes apositive charged quaternary ammonium or, in some cases, a sulfonium orphosphonium ion; a negative charged carboxyl group; and an alkyl group.Zwitterionic surfactants generally contain cationic and anionic groupswhich ionize to a nearly equal degree in the isoelectric region of themolecule and which can develop strong “inner-salt” attraction betweenpositive-negative charge centers. Examples of such zwitterionicsynthetic surfactants include derivatives of aliphatic quaternaryammonium, phosphonium, and sulfonium compounds, in which the aliphaticradicals can be straight chain or branched, and wherein one of thealiphatic substituents contains from 8 to 18 carbon atoms and onecontains an anionic water solubilizing group, e.g., carboxy, sulfonate,sulfate, phosphate, or phosphonate.

Betaine and sultaine surfactants are exemplary zwitterionic surfactantsfor use herein. A general formula for these compounds is:

wherein R¹ contains an alkyl, alkenyl, or hydroxyalkyl radical of from 8to 18 carbon atoms having from 0 to 10 ethylene oxide moieties and from0 to 1 glyceryl moiety; Y is selected from the group consisting ofnitrogen, phosphorus, and sulfur atoms; R² is an alkyl or monohydroxyalkyl group containing 1 to 3 carbon atoms; x is 1 when Y is a sulfuratom and 2 when Y is a nitrogen or phosphorus atom, R³ is an alkylene orhydroxy alkylene or hydroxy alkylene of from 1 to 4 carbon atoms and Zis a radical selected from the group consisting of carboxylate,sulfonate, sulfate, phosphonate, and phosphate groups.

Examples of zwitterionic surfactants having the structures listed aboveinclude:4-[N,N-di(2-hydroxyethyl)-N-octadecylaonio]-butane-1-carboxylate;5-[S-3- hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-1-sulfate;3-[P,P-diethyl-P-3,6,9-trioxatetracosanephosphonio]-2-hydroxypropane-1-phosphate;3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropyl-ammonio]-propane-1-phosphonate;3-(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate;3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxy-propane-1-sulfonate;4-[N,N-di(2(2-hydroxyethyl)-N(2-hydroxydodecyl)ammonio]-butane-1-carboxylate;3-[S-ethyl-S-(3-dodecoxy-2-hydroxypropyl)sulfonio]-propane-1-phosphate;3-[P,P-dimethyl-P-dodecylphosphonio]-propane-1-phosphonate; andS[N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxy-pentane-1-sulfate.The alkyl groups contained in said detergent surfactants can be straightor branched and saturated or unsaturated.

The zwitterionic surfactant suitable for use in the present compositionsincludes a betaine of the general structure:

These surfactant betaines typically do not exhibit strong cationic oranionic characters at pH extremes nor do they show reduced watersolubility in their isoelectric range. Unlike “external” quaternaryammonium salts, betaines are compatible with anionics. Examples ofsuitable betaines include coconut acylamidopropyldimethyl betaine;hexadecyl dimethyl betaine; C₁₂₋₁₄ acylamidopropylbetaine; C₈₋₁₄acylamidohexyldiethyl betaine; 4-C₁₄₋₁₆acylmethylamidodiethylammonio-1-carboxybutane; C₁₆₋₁₈acylamidodimethylbetaine; C₁₂₋₁₆ acylamidopentanediethylbetaine; andC₁₂₋₁₆ acylmethylamidodimethylbetaine.

Sultaines useful in the present invention include those compounds havingthe formula (R(R¹)₂ N⁺R²SO³⁻, in which R is a C₆-C₁₈ hydrocarbyl group,each R¹ is typically independently C₁-C₃ alkyl, e.g., methyl, and R² isa C₁-C₆ hydrocarbyl group, e.g., a C₁-C₃ alkylene or hydroxyalkylenegroup.

A typical listing of zwitterionic classes, and species of thesesurfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin andHeuring on Dec. 30, 1975. Further examples are given in “Surface ActiveAgents and Detergents” (Vol. I and II by Schwartz, Perry and Berch).Each of these references are herein incorporated in their entirety.

In some embodiments, the composition or detergent composition disclosedherein is free of a zwitterionic surfactant.

Gemini Surfactants

While conventional surfactants generally have one hydrophilic group andone hydrophobic group, a Gemini surfactant has at least two hydrophobicgroups and at least two hydrophilic groups. These surfactants have thegeneral formula: A1-G-A2 and get their name because they comprise twosurfactant moieties (A1, A2) joined by a spacer (G), wherein eachsurfactant moiety (A1, A2) has a hydrophilic group and a hydrophobicgroup. Generally, the two surfactant moieties (A1, A2) are the same, butthey can be different.

The Gemini surfactants may be anionic, nonionic, cationic or amphoteric.The hydrophilic and hydrophobic groups of each surfactant moiety (A1,A2) may be any of those known to be used in conventional surfactantshaving one hydrophilic group and one hydrophobic group. For example, atypical nonionic Gemini surfactant, e.g., a bis-polyoxyethylene alkylether, would contain two polyoxyethylene alkyl ether moieties. Eachmoiety would contain a hydrophilic group, e.g., polyethylene oxide, anda hydrophobic group, e.g., an alkyl chain.

Anionic and nonionic Gemini surfactants include those of the formula:

wherein R³⁰ is independently C₁ to C₂₂ alkyl, R³⁴—C(O)—, or R³⁴—B—R³⁵—,wherein R³⁴ is C₁ to C₂₂ alkyl, R³⁵ is C₁ to C₁₂ alkyl, and B is anamide group, —C(O)N(R³⁶)—, an amino group —N(R³⁶)—, a carboxyl group—C(O)—O—, a carbonyl group, or a polyether group —(EO)_(a)(PO)_(b)—,wherein EO represents ethyleneoxy radicals, PO represents propyleneoxyradicals, a and b are numbers of from 0 to 100, a is preferably fromabout 0 to about 30 and b is preferably from about 0 to 10, wherein aplus b is at least one, and the EO and PO radicals can be randomly mixedor in discrete blocks, and R³⁶ is hydrogen or C₁ to C₆ alkyl.

R³¹ is independently hydrogen or C₁ to C₂₂ alkyl; R³² is independently aC₁-C₁₀ alkyl, —O—, an amide group —C(O)N(R₆)—, a polyether group—O(EO)_(a) (PO)_(b)—, —R³⁷-D-R³⁷ , or -D-R³⁷-D-, wherein R³⁷ isindependently a C₁-C₆ alkyl and D is —O—, —S—, an amide group—C(O)N(R³⁶)—, or an amino group —N(R³⁶)—, wherein R³⁶, a and b are asdefined above, and t is independently 0 or 1.

Z is independently hydrogen, —SO₃Y, —P(O)(OY)₂, —COOY, —CH₂COOY,—CH₂CH(OH)CH₂SO₃Y and when R³² is not a polyether, Z is also —OSO₃Y, and—OP(O)(OY)₂; wherein Y is hydrogen, alkali metal such as sodium andpotassium; alkaline earth metal such as magnesium and calcium; ammonium;or organic base salt such as monoethanolamine, diethanolamine,triethanolamine, triethylamine, trimethylamine, N-hydroxyethylmorpholine, and the like.

A1 or A2 is independently a straight chain or branched C₁ to C₆ alkyl,an O—R₅—O— group or aryl; preferably phenyl; R³³ is a bond, an arylgroup such as a phenyl or diphenyl group, a C₁ to C₁₀ alkyl group,preferably a C₁ to C₄ alkyl group, most preferably methylene, —C≡C—,—O—, —S—, —S—S—, —N(R³⁶)—, —R³⁵O—, —R³⁵O(EO)_(a)(PO)_(b)—, -D₁—R³⁸-D₁-or —R³⁸-D₁—R³⁸—, wherein R³⁸ is independently a C₁-C₁₀ alkyl group,—C(O)—,—R³⁵O(EO)_(a)(PO)_(b)—, —O—R³⁵—O—, or aryl, e.g., phenyl, and D₁is independently —O—, —S—, —S—S—, —SO₂—, —C(O)—, a polyether group—O(EO)_(a)(PO)_(b)—, an amide group —C(O)N(R³⁶)—, an amino group—N(R³⁶)—, —O—R₅—O—, or aryl wherein R³⁵, R³⁶, a and b are as definedabove.

On the formulae of this disclosure, the term “alkali” includessubstituted alkali, especially the hydroxy substituted derivativesthereof and straight as well as branched chains. When Z is hydrogen, thegemini surfactants are nonionic.

Other Gemini surfactants specifically useful in the present disclosureinclude gemini anionic or nonionic surfactants of the formulae:

wherein R_(c) represents aryl, preferably phenyl. R³¹, R³³, R³⁴, and Zare as defined above. a and b are numbers of from 0 to 100, a ispreferably from about 0 to about 30 and b is preferably from about 0 to10, wherein a plus b is at least one, and the EO and PO radicals can berandomly mixed or in discrete blocks.

The primary hydroxyl group of these surfactants can be readilyphosphated, sulfated or carboxvlated by standard techniques.

In some embodiments, the composition or detergent composition disclosedherein is free of a Gemini surfactant.

As used herein, the term “substantially free”, “free” or “free of”refers to compositions completely lacking the component or having such asmall amount of the component that the component does not affect theperformance of the composition. The component may be present as animpurity or as a contaminant and shall be less than 0.5 wt-%. In anotherembodiment, the amount of the component is less than 0.1 wt-% and in yetanother embodiment, the amount of component is less than 0.01 wt-%.

The term “weight percent”, “wt-%”, “percent by weight”, “% by weight”,and variations thereof, as used herein, refer to the concentration of asubstance as the weight of that substance divided by the total weight ofthe composition and multiplied by 100. It is understood that, as usedhere, “percent”, “%”, and the like are intended to be synonymous with“weight percent”, “wt-%”, etc.

EXAMPLES

Embodiments of the present invention are further defined in thefollowing non-limiting Examples. It should be understood that theseExamples, while indicating certain embodiments of the invention, aregiven by way of illustration only. From the above discussion and theseExamples, one skilled in the art can ascertain the essentialcharacteristics of this invention, and without departing from the spiritand scope thereof, can make various changes and modifications of theembodiments of the invention to adapt it to various usages andconditions. Thus, various modifications of the embodiments of theinvention, in addition to those shown and described herein, will beapparent to those skilled in the art from the foregoing description.Such modifications are also intended to fall within the scope of theappended claims.

Example 1

General Scheme to Synthesize Exemplary Di-cationic Compounds ContainingTwo Quaternary Groups:

Exemplary di-cationic compounds containing two quaternary groups asdisclosed herein were synthesized, by aza Michael addition reactionbetween a primary amine (1 mole) and α,β-unsaturated carbonyl compound,an activated olefin, containing at least one quaternary group (at least2 moles). The generic synthesis reaction scheme for preparation ofdisclosed di-cationic compounds is shown in FIG. 2.

In FIG. 2, R¹¹ is R¹ or R¹—Z—(CH₂)_(m)—; R¹ is an unsubstituted orsubstituted, linear or branched C₁-C₃₀ alkyl, cyclic alkyl, alkenyl, oralkynyl group; Z is NH or O; R² is H, CH₃, or an unsubstituted, linearor branched C₂-C₁₀ alkyl, alkenyl, or alkynyl group; m is an integer of1 to 4; and n is an integer of 1-20.

The reaction shown in FIG. 2 can be carried out in water at 80° C. Theprogression of this reaction is monitored by ESI-MS and/or NMRspectroscopy for consumption of the monomer. The reaction is typicallystopped at time when a yield of about 98% for the diquat product isobtained. The synthesized compounds in the following Examples were madeaccording to this scheme, except the reactants were different in each ofthe Examples as set forth in further detailed in each Example.

Example 2

Synthesis of3,3′-((3,3′-(octylazanediyl)bis(propanoyl))bis(azanediyl)bis(N,N,N-trimethylpropan-1-aminium)chloride (I)

In this Example, (3-acrylamidopropyl) trimethylammonium chloride (APTAC,75%, 30 grams, 0.10 mol) was charged into a 250-mL three-necked roundbottom flask (RBF) equipped with an overhead stirrer, temperature probe,and condenser. Benzyltrimethylammonium hydroxide (0.9 grams, 10%, 0.0005mol) and water (41 g) were added into the flask. Octylamine (7 grams,99%, 0.053 mol) was then added portion wise to the well-stirred reactionmixture. The resulting suspension was stirred at 80° C. overnight. Asthe reaction proceeded to completion, the suspension turned into a clearyellowish solution. The resulting (˜37 wt %) aqueous solution of thediquat compound,3,3′-((3,3′-(octylazanediyl)bis(propanoyl))bis(azanediyl))bis(N,N,N-trimethylpropan-1-aminium)chloride (referred as compound I), was stored in the container. Massspectrometry (+ESI-MS) confirmed synthesis of the di-cationic compoundI: calc. [M-2Cl⁻]²⁺ 235.73, found 235.7241; calc. [M—Cl⁻]⁺ 506.42, found506.4182.

Example 3

Synthesis of3,3′-((3,3′-(dodecylazanediyl)bis(propanoyl))bis(azaneditl))bis(N,N,N-trimethylpropan-1-aminium)chloride (II)

In this Example, (3-acrylamidopropyl) trimethylammonium chloride (APTAC,75%, 30 grams, 0.10 mol) was charged into a 250-mL three-necked RBFequipped with an overhead stirrer, temperature probe, and condenser.Benzyltrimethylammonium hydroxide (0.9 grams, 10%, 0.0005 mol) and water(63 g) were added into the flask. Dodecylamine (10 grams, 98%, 0.053mol) was then added portion wise to the well-stirred reaction mixture.The resulting suspension was stirred at 80° C. overnight. As thereaction proceeded to completion, the suspension turned into a clearyellowish solution. The resulting (˜31 wt %) aqueous solution of thediquat compound,3,3′-((3,3′-(dodecylazanediyl)bis(propanoyl))bis(azanediyl))bis(N,N,N-trimethylpropan-1-aminium)chloride (referred as compound II) was used as is. Mass spectrometry(+ESI-MS) confirmed synthesis of the diquat compound (II): calc.[M-2Cl⁻]²⁺ 263.76, found 263.7554; calc. [M—Cl⁻]⁺ 562.48, found562.4806.

Example 4

Synthesis of 3,3′-((3,3′-(hexadecylazanediyl)bis(propanoyl))bis(azanediyl))bis(N,N,N-trimethylpropan-1-aminium)chloride (III)

In this Example, (3- acrylamidopropyl) trimethylammonium chloride(APTAC, 75%, 41 grams, 0.149 mol) was charged into a 250-mL three-neckedRBF equipped with an overhead stirrer, temperature probe, and condenser.Benzyltrimethylammonium hydroxide (0.9 grams, 10%, 0.0005 mol) and water(100 g) were added into the flask. Hexadecylamine (20 grams, 90%, 0.0745mol) was then added portion wise to the well-stirred reaction mixture.The resulting suspension was stirred at 80° C. overnight. As thereaction proceeded to completion, the suspension turned into a clearyellowish solution. The resulting (˜30 wt %) aqueous solution of thediquat compound,3,3′-((3,3′-(hexadecylazanediyl)bis(propanoyl))bis(azanediyl))bis(N,N,N-trimethylpropan-1-aminium) chloride (referred as compound III), was used as is. Massspectrometry (+ESI/MS) confirmed synthesis of the diquat compound (III):calc. [M-2Cl⁻]²⁺ 291.79, found 291.7870; calc. [M—Cl⁻]⁺ 618.54, found618.5439.

Example 5

Synthesis of3,3′-((3,3′-(octylazanediyl)bis(propanoyl)bis(azanediyl))bis(N,N,N-trimethylpropan-1-aminium)chloride (IV)

In this Example, (3-acrylamidopropyl) trimethylammonium chloride (APTAC,75%, 40 grams, 0.145 mol) was charged into a 250-mL three-necked RBFequipped with an overhead stirrer, temperature probe, and condenser.Benzyltrimethylammonium hydroxide (0.9 grams, 10%, 0.0005 mol) and water(100 g) were added into the flask. Octadecylamine (20 grams, 98%, 0.072mol) was then added portion wise to the well-stirred reaction mixture.The resulting suspension was stirred at 80° C. overnight. As thereaction proceeded to completion, the suspension turned into a clearyellowish solution. The resulting (˜31 wt %) aqueous solution of thediquat compound,3,3′-((3,3′-(octylazanediyl)bis(propanoyl))bis(azanediyl))bis(N,N,N-trimethylpropan-1-aminium)chloride (referred as compound IV), was used as is. Mass spectrometry(+ESI-MS) confirmed synthesis of the diquat compound IV: calc.[M-2Cl⁻]²⁺ 305.80, found 305.8014; calc. [M-Cl⁻]⁺ 646.58, found648.5791.

Example 6

Synthesis of 3,3′-(3,3′-(octadec-9-en-1-ylazanediyl) bis(propanoyl))bis(azanediyl)) bis(N,N,N-trimethylpropan-1-aminium) chloride (V)

In this Example, (3-acrylamidopropyl) trimethylammonium chloride (APTAC,75%, 30 grams, 0.109 mol) was charged into a 250-mL three-necked RBFequipped with an overhead stirrer, temperature probe, and condenser.Benzyltrimethylammonium hydroxide (0.25 grams, 10%, 0.0001 mol) andwater (70 g) were added into the flask. Oleylamine (15 grams, 95%, 0.053mol) was then added portion wise to the well-stirred reaction mixture.The resulting suspension was stirred at 80° C. overnight. As thereaction proceeded to completion, the suspension turned into a clearyellowish solution. The resulting (˜32 wt %) aqueous solution of thediquat compound, 3,3′-((3,3′-(octadec-9-en-1-ylazanediyl)bis(propanoyl)) bis(azanediyl)) bis(N,N,N-trimethylpropan-1-aminium)chloride (referred as V), was used as is. Mass spectrometry (+ESI-MS)confirmed synthesis of the diquat compound: calc. [M-2Cl⁻]²⁺ 304.80,found 304.7949; calc. [M—Cl⁻]⁺ 644.56, found 644.5596.

Exmaple 7

Synthesis of3,3′-((3,3′-((3-(octadec-9-en-1-ylamino)propyl)azanediyl)bis(propanoyl))bis(azanediyl)) bis(N,N,N-trimethylpropan-1-aminium) chloride (VI)

In this Example, (3-acrylamidopropyl) trimethylammonium chloride (APTAC,75%, 42 grams, 0.152 mol) was charged into a 250-mL three-necked RBFequipped with an overhead stirrer, temperature probe, and condenser.Benzyltrimethylammonium hydroxide (0.25 grams, 10%, 0.0001 mol) andwater (130 g) were added into the flask. N-oleylpropanediamine (25grams, 99%, 0.076 mol) was then added portion wise to the well-stirredreaction mixture. The resulting suspension was stirred at 80° C.overnight. As the reaction proceeded to completion, the suspensionturned into a clear yellowish solution. The resulting (˜28 wt %) aqueoussolution of the diquat compound,3,3′-((3,3′-((3-(octadec-9-en-1-ylamino)propyl)azanediyl)bis(propanoyl))bis(azanediyl)) bis(N,N,N-trimethylpropan-1-aminium) chloride (referred asVI), was used as is. Mass spectrometry (+ESI/MS) confirmed synthesis ofthe diquat compound VI: calc. [M-2Cl⁻]²⁺ 333.32, found 333.3238; calc.[M—Cl⁻]⁺ 701.62, found 701.6173.

Example 8

Surface Tension Measurements

Surface tension measurements were conducted on a Tracker tensiometer(Teclis Instruments) at room temperature. Various solutions withdifferent concentrations of the exemplary di-cationic compounds wereprepared, and surface tension measurements were conducted. The surfacetension as a function of concentration of the exemplary di-cationiccompounds were measured and are listed in Table 1.

TABLE 1 Surface tension measurements of the exemplary diquat compounds(I-VI) Concentration Surface Tension (dynes/cm) (%) I II III IV V VI0.010 49.19 53.35 70.43 68.98 69.3  61.78 0.025 44.36 46.29 53.79 53.2954.24 57.85 0.050 35.86 43.64 48.49 50.25 43.95 46.67 0.100 31.85 42.2046.07 50.57 39.81 45.32 0.500 25.1  36.36 45.61 47.13 40.84 44.81

The inventions being thus described, it will be obvious that the samemay be varied in many ways. Such variations are not to be regarded as adeparture from the spirit and scope of the disclosures and all suchmodifications are intended to be included within the scope of thefollowing claims.

The above specification provides a description of the novel compounds,their synthesis and use, and the compositions, products, or articlesthat comprise the disclosed compounds. Since many embodiments can bemade without departing from the spirit and scope of the disclosure, theinvention resides in the claims.

What is claimed is:
 1. A compound according to Formula I:

wherein, X is NH or O; R¹¹ is R¹—Z—(CH₂)_(m)—; R¹ is an unsubstituted orsubstituted linear or branched C₅-C₃₀ alkyl, cyclic alkyl, alkenyl, oralkynyl group; Z is O; R² is H, CH₃, or an unsubstituted linear orbranched C₂-C₁₀ alkyl, alkenyl, or alkynyl group; m is an integer of 1to 4; R³ is absent, an unsubstituted linear C₁-C₃₀ alkylene group, orC(CH₃)₂; Y is —NR⁴R⁵R⁶⁽⁺⁾, or a salt thereof; and R⁴ and R⁵ areindependently a C₁-C₁₀ alkyl group, and R⁶ is a C₁-C₁₀ alkyl, aryl, oris —CH₂-C₆H₅.
 2. The compound according to claim 1, wherein X is NH. 3.The compound according to claim 1, wherein X is O.
 4. The compound ofclaim 1, wherein R¹ is the unsubstituted or substituted linear C₅-C₃₀alkyl, alkenyl, or alkynyl group.
 5. The compound of claim 1, wherein R²is H or CH₃.
 6. The compound of claim 1, wherein Y is —NR⁴R⁵R⁶⁽⁺⁾,N(CH₃)₃ ⁺, or N(CH₃)₂R⁶⁺.
 7. The compound of claim 1, wherein R³ isC(CH₃)₂ or the unsubstituted linear C₂-C₁₀ alkylene group.
 8. Thecompound of claim 1, wherein R¹ is the unsubstituted or substitutedC₅-C₃₀ alkenyl group with at least one trans or cis double bond.
 9. Amethod to synthesize the compound according to claim 1, comprising:contacting a primary amine with an activated olefin having a cationicgroup to generate a compound; wherein the primary amine is R¹¹—NH₂; andwherein the activated olefin is

wherein, X is NH or O; R¹¹ is R¹—Z—(CH₂)_(m)—; R¹ is an unsubstituted orsubstituted linear or branched C₅-C₃₀ alkyl, cyclic alkyl, alkenyl, oralkynyl group; Z is O; R² is H, CH₃, or an unsubstituted linear orbranched C₂-C₁₀ alkyl, alkenyl, or alkynyl group; m is an integer of 1to 4; R³ is absent, an unsubstituted linear C₁-C₃₀ alkylene group, orC(CH₃)₂; Y is —NR⁴R⁵R⁶⁽⁺⁾, or a salt thereof; and R⁴ and R⁵ areindependently a C₁-C₁₀ alkyl group, and R⁶ is a C₁-C₁₀ alkyl, aryl, oris —CH₂—C₆H₅.
 10. The method of claim 9, wherein the contacting step isdone in the presence of a reaction solvent, of a reaction solvent andalkalinity source, of a reaction solvent and acid, or of a reactionsolvent and a catalyst.
 11. The method of claim 10, wherein the reactionsolvent is water, methanol, ethanol, propanol, glycol, PEG, or a mixturethereof.
 12. The method of claim 9, wherein the contacting step is donein the presence of benzyltrimethylammonium hydroxide.
 13. An article,product, or composition comprising one or more compounds according toFormula I:

wherein, X is NH or O; R¹¹ is R¹—Z—(CH₂)_(m)—; R¹ is an unsubstituted orsubstituted, linear or branched C₅-C₃₀ alkyl, cyclic alkyl, alkenyl, oralkynyl group; Z is O; R² is H, CH₃, or an unsubstituted, linear orbranched C₂-C₁₀ alkyl, alkenyl, or alkynyl group; m is an integer of 1to 4; R³ is absent, an unsubstituted linear C₁-C₃₀ alkylene group, orC(CH₃)₂; Y is —NR₄R₅R₆ ⁽⁺⁾ or a salt thereof; and R⁴ and R⁵ areindependently a C₁-C₁₀ alkyl group, and R⁶ is a C₁-C₁₀ alkyl, aryl, oris —CH₂—C₆H₅.
 14. The article, product, or composition of claim 13,wherein the article, product or composition further comprises a carriersolvent and is an aqueous article, product, or composition.
 15. Thearticle, product, or composition of claim 14, wherein the carriersolvent is water, an alcohol, an alkylene glycol, an alkylene glycolalkyl ether, or a combination thereof.
 16. The article, product, orcomposition of claim 13, wherein the article, product, or compositionfurther comprises a primary alkalinity source and is a detergentcomposition.
 17. The article, product, or composition of claim 16,wherein the article, product, or composition further comprises achelant.
 18. The article, product, or composition of claim 16, whereinthe article, product, or composition further comprises an enzyme. 19.The article, product, or composition of claim 16, wherein the article,product, or composition further comprises an additional detergentcomposition agent.
 20. The article, product, or composition of claim 13,further comprising an additional surfactant, wherein the additionalsurfactant is a nonionic, semi-nonionic, cationic, anionic, amphoteric,zwitterionic, Gemini, surfactant or mixtures thereof.